EP0567819B1 - Aqueous polymer dispersion - Google Patents
Aqueous polymer dispersion Download PDFInfo
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- EP0567819B1 EP0567819B1 EP93105832A EP93105832A EP0567819B1 EP 0567819 B1 EP0567819 B1 EP 0567819B1 EP 93105832 A EP93105832 A EP 93105832A EP 93105832 A EP93105832 A EP 93105832A EP 0567819 B1 EP0567819 B1 EP 0567819B1
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- aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- the present invention further relates to the process for the preparation of such aqueous polymer dispersions and their use as binders and as compositions for the production of coatings and bonds.
- Aqueous polymer dispersions are systems which contain polymer particles dispersed as a disperse phase in an aqueous dispersion medium.
- aqueous polymer dispersions have the property of forming polymer films when the aqueous dispersion medium is evaporated, which is why aqueous polymer dispersions are used in many ways as binders, for example for paints or for coating leather.
- Aqueous polymer dispersions with a high proportion of polymer are particularly advantageous in that, on the one hand, their relatively lower proportion of aqueous dispersion medium means the expense of evaporating the same, e.g. for film formation or for the production of polymer powders, and on the other hand the polymer can be stored and transported in a relatively smaller amount of aqueous phase as the carrier medium.
- a process for the preparation of an aqueous polymer dispersion in which unsaturated monomers are polymerized in a polymerization vessel in accordance with the free-radical aqueous emulsion polymerization process in a manner known per se and an aqueous dispersion of a starting polymer is added, the addition the aqueous dispersion of the starting polymer must be completed before 40% by weight of the total to be polymerized Monomers are polymerized in and may only be carried out at the earliest if the average particle size of the emulsion polymer formed during the polymerization of the monomers has twice the value of the average particle size of the aqueous dispersion of the starting polymer.
- the aqueous dispersion of the starting polymer is preferably not added over a long period of time, but rather all at once.
- a disadvantage of the aqueous polymer dispersions obtainable in this way is that their flow resistance above a solid volume concentration of 50% by volume is not fully satisfactory and, according to the exemplary embodiments, the solid volume concentration is limited to values below 65% by volume.
- US Pat. No. 4,130,523 relates to a process for the preparation of aqueous polymer dispersions, in which aqueous polymer dispersions which have already formed during the polymerization process are removed from the reaction zone, stored and later fed back to the reaction zone as a type of starting polymer dispersion.
- a disadvantage of this process is that it is unsuitable for large-scale implementation.
- US Pat. No. 3,424,706 relates to a process for the preparation of aqueous polymer dispersions, the polymers of which contain at least 70 to 97% by weight of copolymerized vinylidene chloride, in which the polymerization of the monomers takes place with the addition of an aqueous dispersion of a starting polymer.
- US Pat. No. 3,424,706 contains the information to mix the monomers to be polymerized and the aqueous dispersion of the starting polymer with one another and to feed this mixture to the template comprising part of the polymerization batch.
- a disadvantage of this process is that it is limited to monomer mixtures which mainly contain vinylidene chloride.
- the flow resistance above a solids volume concentration of 50% by volume, as well as that which can still be achieved in a satisfactorily flowable state can also be achieved with the aqueous polymer dispersions obtainable by this process Unsatisfactory upper limit of the solid volume concentration.
- the aim of the present invention was therefore to provide aqueous polymer dispersions which are obtainable in a simple, industrially suitable, reproducible and not limited to special monomers manner with an increased solid volume concentration with reduced flow resistance and reduced flocculation content.
- the subject matter of the invention is not limited to the free radical aqueous emulsion polymerization of monomer mixtures composed mainly or exclusively of vinyl and / or vinylidene halides, since it is generally known that the development of the disperse phase in the case of vinyl and / or vinylidene halides different monomers is essential has a more complex appearance.
- the radically polymerizable monomers used include, in particular, monoethylenically unsaturated monomers such as olefins, for example ethylene, vinylaromatic monomers such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms, such as Vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids, preferably having 3 to 6 carbon atoms, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with in general 1 to 12, preferably 1 to 8 and in particular 1 to 4, alkanols, such as, in particular, methyl, ethyl, n
- butyl esters nitriles ⁇ , ⁇ -monoethylenically unsaturated carboxylic acids such as acrylonitrile and C 4-8 conjugate dienes such as 1,3-butadiene and isoprene.
- the monomers mentioned generally form the main monomers which, based on the total amount of the monomers to be polymerized by the free-radical aqueous emulsion polymerization process, normally account for more than 50% by weight.
- Examples of such monomers are ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids and their amides such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamide and methacrylamide, also vinyl sulfonic acid and its water-soluble salts and N- Vinyl pyrrolidone.
- Monomers which usually increase the internal strength of the films in the aqueous polymer dispersion, are generally also copolymerized only in minor amounts, usually 0.5 to 10% by weight, based on the total amount of the monomers to be polymerized.
- Such monomers normally have an epoxy, hydroxy, N-methylol, carbonyl or at least two non-conjugated ethylenically unsaturated double bonds.
- these are N-alkylolamides of ⁇ , ⁇ -monoethylenically unsaturated carboxylic acids having 3 to 10 C atoms and their esters with alcohols having 1 to 4 C atoms, among which the N-methylolacrylamide and the N-methylolmethacrylamide are very particularly preferred, two monomers having vinyl radicals, two monomers having vinylidene radicals and two monomers having alkenyl radicals.
- the di-esters of dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids are particularly suitable, among which in turn acrylic and methacrylic acid are preferably used.
- monomers having two non-conjugated ethylenically unsaturated double bonds are alkylene glycol diacrylate and dimethacrylates such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and propylene glycol diacrylate, divinylbenzene, vinyl methacrylate, allyl acrylate, allyl acrylate, vinyl acrylate or triallyl cyanurate.
- methacrylic acid and acrylic acid-C 1 -C 8 -hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-Hydroxybutyl acrylate and methacrylate and compounds such as diacetone acrylamide and acetylacetoxyethyl acrylate or methacrylate.
- methacrylic acid and acrylic acid-C 1 -C 8 -hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-Hydroxybutyl acrylate and methacrylate and compounds such as diacetone acrylamide and acetylacetoxyethyl acrylate or methacrylate.
- minor amounts, usually 0.01 to 2% by weight, based on the monomers to be polymerized of copolymerizing substances such as tert-dodecyl mercaptan and 3-mercaptopropyltrimethoxysilane can also be cop
- Suitable dispersants are both the protective colloids usually used to carry out free-radical aqueous emulsion polymerizations and emulsifiers.
- Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or copolymers containing vinyl pyrrolidone. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411 to 420. Of course, mixtures of emulsifiers and / or protective colloids can be used.
- emulsifiers are used as dispersants, the relative molecular weights of which, in contrast to the protective colloids, are usually below 1000. They can be anionic, cationic or nonionic in nature. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked with a few preliminary tests if in doubt. In general, anionic emulsifiers are compatible with one another and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with one another.
- Common emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C 4 to C 9 ), ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C 8 to C 36 ), as well as alkali and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C 12 to C 18 ) and ethoxylated alkyl phenols (EO degree: 3 to 50, alkyl radical: C 4 to C 9 ), of alkyl sulfonic acids (alkyl radical: C 12 to C 18 ) and of alkylarylsulfonic acids (alkyl radical: C 9 to C 18 ). Further suitable emulsifiers can be found in Houben-Weyl, Methods
- R 1 and R 2 are hydrogen or C 4 - to C 24 -alkyl and are not simultaneously hydrogen
- X and Y can be alkali metal ions and / or ammonium ions.
- R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 carbon atoms or hydrogen, and in particular having 6, 12 and 16 carbon atoms, where R 1 and R 2 are not both hydrogen at the same time.
- X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred.
- Compounds I in which X and Y are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is hydrogen or R 1 are particularly advantageous.
- Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (trademark of the Dow Chemical Company).
- the compounds I are preferably used on their own and particularly preferably in a mixture with ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C 8 to C 36 ) as dispersants.
- the compounds I are generally known, for example from US Pat. No. 4,269,749, and are commercially available.
- the aqueous polymer final dispersion according to the invention advantageously contains 1 to 3% by weight of surface-active substances, based on the mass of the final polymer.
- Free radical polymerization initiators are all those which are capable of initiating a free radical aqueous emulsion polymerization. It can be both peroxides, for example alkali metal peroxydisulfates, as well as azo compounds.
- Combined systems which are composed of at least one organic reducing agent and at least one peroxide and / or hydroperoxide, for example tert.-butyl hydroperoxide and the sodium metal salt of hydroxymethanesulfinic acid or hydrogen peroxide and ascorbic acid, and very particularly preferred combined systems which are moreover a small amount contain a metal compound soluble in the polymerization medium, the metallic component of which can occur in several valence stages, for example ascorbic acid / iron (II) sulfate / hydrogen peroxide, the sodium metal salt of hydroxymethanesulfinic acid, sodium sulfite, sodium hydrogen sulfite or sodium metal disulfite and instead of hydrogen peroxide also frequently being used instead of ascor
- Butyl hydroperoxide or alkali metal peroxydisulfates and / or ammonium peroxydisulfate can be used.
- a water-soluble iron (II) salt instead of a water-soluble Fe (II) salt, a combination of water-soluble Fe / V salts is often used.
- the amount of free-radical initiator systems used is preferably 0.1 to 2% by weight, based on the total amount of the monomers to be polymerized.
- the manner in which the free-radical initiator system is added to the polymerization vessel in the course of the free-radical aqueous emulsion polymerization according to the invention is of minor importance with regard to the success of the process according to the invention.
- the initiator system can either be completely introduced into the polymerization vessel or, depending on its consumption, can be added continuously or in stages in the course of the free-radical aqueous emulsion polymerization. Specifically, this depends on the chemical nature of the initiator system and on the polymerization temperature in a manner known per se to the person skilled in the art.
- Polymerization pressure and polymerization temperature are also of minor importance. In general, temperatures between room temperature and 100 ° C, preferably at temperatures of 50 to 95 ° C. The application of increased or reduced pressure is possible, so that the polymerization temperature also exceed 100 ° C and can be up to 130 ° C. Volatile monomers such as ethylene, butadiene or vinyl chloride are preferably polymerized under elevated pressure. To regulate the pH of the polymerization medium, ammonia, for example, can be added during the free radical aqueous emulsion polymerization according to the invention.
- the free-radically polymerizable monomers mentioned as suitable for the free radical aqueous emulsion polymerization according to the invention are suitable not only as constituents of the monomer mixture to be polymerized according to the invention. Rather, they are suitable in the same way as the polymerization initiators recommended for the radical aqueous emulsion polymerization according to the invention, the compounds regulating the molecular weight and the pH-regulating agents, also as constituents of the starting polymers I, II or the starting polymer dispersions containing them, the monomers, Controller and initiator composition for the preparation of the aqueous polymer starting dispersions I, II with which those for the process according to the invention can be congruent as well as different.
- the statements made here also apply in a figurative sense to the surface-active substances to be used for the preparation of the aqueous polymer starting dispersions I, II.
- Aqueous starting polymer dispersions I can be obtained in a simple manner by combining n aqueous starting polymer dispersions II, the particle diameter distribution functions of which preferably do not substantially overlap, in a manner defined by definition. From an application point of view, n is preferably in the range from 2 to 10, preferably in the range from 2 to 5.
- the preparation of aqueous polymer starting dispersions II is known per se. Appropriate teachings are e.g. B. in Houben-Weyl, Methods of Organic Chemistry, Volume E 20, Part I, Macromolecular Substances, Georg-Thieme Verlag, Stuttgart, 1987, pages 248 to 268.
- the aqueous polymer dispersion II are in a particularly simple manner, for. B. obtainable by the aqueous phase, the monomers, the free radical initiators (normally 0.1 to 5 wt .-%, based on the amount of the starting monomers to be polymerized) and dispersants (usually 10 to 50 wt .-%, based on the amount of starting monomers to be polymerized) mixed together at a low temperature and, after mixing, heated to the polymerization temperature and polymerized (increasing amounts of dispersant usually result in a decreasing weight average particle diameter).
- the initial charge comprises essentially all of the components, but the polymerization initiator is fed continuously after heating to the reaction temperature while maintaining the same.
- coarse-particle aqueous polymer starting dispersions II can be obtained, for example, by placing a finely divided aqueous polymer starting dispersion II in a polymerization vessel, heating to the polymerization temperature and then further monomers, usually pre-emulsified in an aqueous medium, and maintaining the initiator Feeds the polymerization temperature into the polymerization vessel.
- the amount of emulsifier added in the context of the aqueous monomer emulsion is such that the total amount of dispersant contained in the resulting coarsely divided aqueous polymer starting dispersion II, based on the resulting coarse starting polymer II, 0.5 to 5, preferably 0.5 to 3% by weight. is.
- the particle coarsening to be achieved is essentially determined by the quantitative ratio of the finely divided starting polymer II particles contained in the initial charge and the monomers supplied.
- the process of producing a relatively finely divided aqueous polymer starting dispersion II and the process of coarsening can merge seamlessly.
- the information about weight-average polymer particle diameters and quotients (d 90 -d 10 ) / d 50 of the aqueous polymer starting dispersions always refer to determinations by means of the analytical ultracentrifuge (W. Gurchtle, Makromolekulare Chemie, Vol. 185 (1984), pp. 1025-1039 ).
- the determinations of the polymer particle size distribution of the aqueous Final polymer dispersions were determined using the so-called coupling PSD technique in the analytical ultracentrifuge (cf. W. Gurchtle, Angewandte Makromolekulare Chemie 162 (1988) 35-42 (No. 2735)).
- aqueous polymer starting dispersions I which are based on aqueous polymer starting dispersions II with a d ⁇ w, i ⁇ 100 nm contain only those whose d ⁇ w, i are exclusively in the range from ⁇ 20 nm to ⁇ 100 nm, very particularly preferably exclusively in the range from ⁇ 30 to ⁇ 60 nm.
- aqueous polymer starting dispersions I which contain only such aqueous polymer starting dispersions II that the difference between d ⁇ w, ⁇ 100 and d ⁇ w, i , where d ⁇ w, i here is the weight-average particle diameter of the aqueous polymer starting dispersion II contained in the aqueous polymer starting dispersion I, the value above 100 nm of which is closest to 100 nm, is at least 60, preferably at least 100 nm.
- those aqueous polymer starting dispersions I are preferably used for which all k values are in the range 0.9 to 1.1 and all k 'values are in the range 0.75 to 3, preferably in the range 0.9 to 1.5 . It is particularly advantageous if all values k and k 'for the at least one aqueous polymer starting dispersion I used are about 1.
- V ⁇ 100 in the at least one aqueous polymer starting dispersion I to be added, based on the sum of all V i contained therein, is advantageously 0.5 to 5% by volume.
- the content of dispersant in the at least one aqueous polymer starting dispersion I is normally 0.5 to 5% by weight, based on the amount of the starting polymer I contained therein.
- the aqueous polymer final dispersions according to the invention are obtainable by introducing the total amount of the at least one aqueous polymer starting dispersion I to be added into the polymerization vessel before the free-radical aqueous emulsion polymerization according to the invention is started and the free-radical aqueous emulsion polymerization of the at least one monomer to be radically polymerized by the feed process.
- the monomers to be polymerized by free radicals are preferably supplied pre-emulsified in the aqueous phase, the amount of the emulsifier used in this regard, based on the amount of the emulsified monomers, advantageously being 0.5 to 3% by weight.
- some polymerization initiator and a small part of the at least one monomer to be polymerized are placed in the polymerization vessel, the mixture onto which Heat the polymerization temperature and then, while maintaining the polymerization, allow the remaining monomers and further polymerization initiator to run synchronously into the polymerization vessel in such a way that from the start of the free-radical aqueous emulsion polymerization the at least one free-radically polymerizable monomer is fed into the polymerization vessel in such a way that the polymerization conversion occurs at any time during the addition
- the total amount of monomers supplied to the polymerization vessel beforehand is at least 80, preferably at least 90, mol%, the initiator feed preferably being extends somewhat beyond the duration of the monomer feed.
- the radical aqueous emulsion polymerization according to the invention can also be carried out in such a way that the initial charge contains only the aqueous polymer starting dispersion I, is heated to the polymerization temperature and then initiates the polymerization initiator and monomer feed simultaneously starting the polymerization.
- additional dispersing agent e.g. B. spatially separated or as part of the monomer emulsion.
- the procedure according to the invention is such that the free-radical aqueous emulsion polymerization in the polymerization vessel at any time from the start of the invention contained amount of dispersant, based on the sum of the masses of starting polymer I and monomers to be polymerized, which have already been fed to the polymerization vessel, is 0.5 to 5% by weight.
- composition of the monomers to be fed can change in the course of the aqueous radical emulsion polymerization according to the invention during the feed process.
- the inflow can take place stepwise or continuously or according to the gradient procedure.
- the monomer feed is preferably carried out continuously.
- stirring is preferably continued for a few hours while maintaining the polymerization temperature.
- This can be followed by customary measures for removing residual monomers, adjusting a different pH or other methods for post-stabilization, including the subsequent addition of dispersants.
- the various possible, usually spatially separate, feeds can be mixed with one another immediately before entering the polymerization vessel.
- aqueous polymer dispersions according to the invention which normally have Newtonian flow behavior. Below a solid volume concentration of 50% by volume, the influence of the particle size distribution on the flow resistance decreases increasingly. As described, the aqueous polymer dispersions according to the invention are generally obtained with fully satisfactory reproducibility and in the absence of flocculation with solid volume concentrations of up to 75% by volume in a manner which is simple to implement on an industrial scale.
- aqueous polymer final dispersions according to the invention display their advantageous properties at solids volume concentrations above 65% by volume, which is why such polymer final dispersions are preferred are. They are generally suitable as binders and as compositions for the production of coatings and bonds, in this regard additional auxiliaries such as film-forming aids, fillers or plasticizers can be added in a manner known per se.
- the dispersions ADI (1) to ADI (9) were prepared in a simple manner by combining various dispersions ADII obtained in Example 1, the amounts of the dispersions ADII used from Example 1 used being dimensioned such that the resulting dispersions ADI Starting polymers APII with the volume fractions shown in Table 1 below (% by volume, based on the total volume of all starting polymers APII contained in the respective dispersion ADI) were contained. Accordingly, the ADI solids content was approximately 40% by weight in all cases.
- APII (2) APII (3)
- APII (4) APII (5)
- APII (6) APII (7)
- APII (8) ADI (1) 0.7 3.1 3.9 6.5 10.0 17.1 23.7 35.0
- ADI (2) 0.8 - - - - - 44.8 54.4 ADI (3) 0.6 - - - 22.4 - 34.8 42.2
- ADI (4) - 1.24 - - 22.26 - 34.6 41.9 ADI (5) 0.81 - - - - 22.4 30.96 45.73 ADI (6) 2.0 - - - - 22.2 30.6 45.2 ADI (7) 3.0 - - - - 21.9 30.3 44.8 ADI (8) 1.9 - - - - - - 98.1 ADI (9) 4.5 - - - - - 21.7 33.7 40.1
- a mixture of water, a 30% strength by weight aqueous hydrogen peroxide solution, a polymer starting dispersion I from Example 2 and part of feed I was heated to 70 ° C., and then simultaneously the remaining amount of feed I (within 3 h) and Feed II (the first 10% by weight in 20 min, the remaining 90% by weight within 220 min) was added continuously while maintaining the polymerization temperature. The mixture was then stirred at 70 ° C for 1 h.
- Table 2 gives the respective composition of the initial charge (quantities in grams), the solids content and the volume concentration of the final dispersion (% by weight and% by volume) as well as the dynamic viscosities ⁇ 60 and ⁇ 60.9 from to a uniform 60%. % or 60.9% by volume of dilute aqueous polymer dispersions in mPas again, the ⁇ determinations according to DIN 53019 being carried out at 23 ° C. and a shear rate of 487 s -1 .
- Table 3 also shows the final polymer particle size distribution (% by weight of the particles of the final polymer whose particle diameter is ⁇ X nm, where X is an element from the amount ⁇ 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1200 ⁇ is).
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Description
Die vorliegende Erfindung betrifft eine wäßrige Polymerisatenddispersion, die eine Feststoffvolumenkonzentration von wenigstens 50 Vol.-% aufweist (Feststoffvolumen = Feststoffmasse dividiert durch Feststoffdichte), dadurch erhältlich, daß man wenigstens ein von Vinyl- und Vinylidenhalogeniden verschiedenes radikalisch polymerisierbares Monomeres unter Zusatz wenigstens einer wäßrigen Polymerisatausgangsdispersion I in einem Polymerisationsgefäß nach dem Verfahren der radikalischen wäßrigen Emulsionspolymerisation in Gegenwart von Dispergiermitteln und radikalischen Polymerisationsinitiatoren mit der Maßgabe polymerisiert, daß
- A) die in der wenigstens einen zugesetzten wäßrigen Polymerisatausgangsdispersion I enthaltene Masse an Polymerisat, bezogen auf die Gesamtmasse, gebildet aus der Masse des wenigstens einen radikalisch polymerisierbaren Monomeren und der in Form der wäßrigen Polymerisatausgangsdispersion I zugesetzten Masse an Polymerisat, 1 bis 10, vorzugsweise 1 bis 5 % beträgt,
- B) die wenigstens eine zugesetzte wäßrige Polymerisatausgangsdispersion I so wie eine durch Zusammengeben von n wäßrigen Polymerisatausgangsdispersionen II erhaltene wäßrige Polymerisatdispersion beschaffen ist, bei welcher das Zusammengeben mit der Maßgabe erfolgte, daß
- a) n eine ganze Zahl ≧ 2 ist,
- b) der gewichtsmittlere Teilchendurchmesser der in den jeweiligen wäßrigen Polymerisatausgangsdispersionen II in disperser Verteilung vorliegenden Ausgangspolymerisatteilchen für jede wäßrige Polymerisatausgangsdispersion II im Bereich > 0 bis 400 nm liegt,
- c) der gewichtsmittlere Teilchendurchmesser der Ausgangspolymerisatteilchen wenigstens einer wäßrigen Polymerisatausgangsdispersion II im Bereich > 0 bis 100 nm liegt,
- d) die wäßrigen Polymerisatausgangsdispersionen II eine monomodale Verteilung der Durchmesser der in ihnen enthaltenen Ausgangspolymerisatteilchen aufweisen, die so beschaffen ist, daß wenn dx den Durchmesser definiert, unterhalb dessen der Teilchendurchmesser von X Gew.-% aller in der jeweiligen wäßrigen Ausgangsdispersion II vorhandenen Ausgangspolymerisatteilchen liegt, der Quotient (d90-d10)/d50 einen Wert von 0,1 bis 0,6 annimmt,
- e) zwischen dem durch Division der in der i-ten wäßrigen Polymerisatausgangsdispersion II enthaltenen Masse des i-ten Ausgangspolymerisats II mit der Massendichte des i-ten Ausgangspolymerisats II erhältlichen Volumen Vi und dem in entsprechender Weise bestimmten Volumen Vj, unter der Voraussetzung, daß sowohl der gewichtsmittlere Teilchendurchmesser der in der i-ten wäßrigen Polymerisatausgangsdispersion II enthaltenen Ausgangspolymerisatteilchen (
- f) zwischen dem über die Gesamtmenge aller wäßrigen Polymerisatausgangsdispersionen II, die einen gewichtsmittleren Teilchendurchmesser der in ihnen enthaltenen Ausgangspolymerisatteilchen im Bereich von > 0 bis ≦ 100 nm aufweisen, ermittelten gewichtsmittleren Teilchendurchmesser der in dieser Gesamtmenge enthaltenen Ausgangspolymerisatteilchen (
- Vi =
- Masse des in der i-ten wäßrigen Polymerisatausgangsdispersion II enthaltenen Ausgangspolymerisats dividiert durch dessen Massendichte,
- V≦100 =
- Masse des in der Gesamtmenge aller wäßrigen Polymerisatausgangsdispersionen II, die einen gewichtsmittleren Teilchendurchmesser der in ihnen enthaltenen Ausgangspolymerisatteilchen im Bereich von > 0 bis ≦ 100 nm aufweisen, enthaltenen Ausgangspolymerisats dividiert durch dessen Massendichte,
- g) V≦100, bezogen auf die Summe aller Vi, 0,3 bis 10 Vol.-% beträgt und
- h) die Differenz zwischen dem kleinsten und dem größten gewichtsmittleren Teilchendurchmesser
- C) die Gesamtmenge der wenigstens einen zuzusetzenden wäßrigen Polymerisatausgangsdispersion I vor Beginn der radikalischen wäßrigen Emulsionspolymerisation ins Polymerisationsgefäß vorgelegt wird und
- D) die radikalische wäßrige Emulsionspolymerisation des wenigstens einen radikalisch polymerisierbaren Monomeren nach dem Zulaufverfahren mit der Maßgabe erfolgt, daß
- ab Beginn der radikalischen wäßrigen Emulsionspolymerisation der Zulauf des wenigstens einen radikalisch polymerisierbaren Monomeren ins Polymerisationsgefäß so erfolgt, daß zu jedem Zeitpunkt des Zulaufs der Polymerisationsumsatz der bereits zuvor dem Polymerisationsgefäß insgesamt zugeführten Monomeren wenigstens 80 mol.-% beträgt und
- die zu jedem Zeitpunkt ab Beginn der radikalischen wäßrigen Emulsionspolymerisation im Polymerisationsgefäß enthaltene Menge an Dispergiermittel, bezogen auf die Summe der dem Polymerisationsgefäß bereits zugeführten Massen an Ausgangspolymerisat I und zu polymerisierenden Monomeren, 0,5 bis 5 Gew.-% beträgt.
- A) the mass of polymer contained in the at least one added aqueous polymer starting dispersion I, based on the total mass, formed from the mass of the at least one free-radically polymerizable monomer and the mass of polymer added in the form of the aqueous polymer starting dispersion I, 1 to 10, preferably 1 is up to 5%,
- B) the at least one added aqueous polymer dispersion I as well as an aqueous polymer dispersion obtained by combining n aqueous polymer dispersions II, in which the combination was carried out with the proviso that
- a) n is an integer ≧ 2,
- b) the weight-average particle diameter of the starting polymer particles present in disperse distribution in the respective aqueous polymer starting dispersions II for each aqueous polymer starting dispersion II is in the range> 0 to 400 nm,
- c) the weight-average particle diameter of the starting polymer particles of at least one aqueous starting polymer dispersion II is in the range> 0 to 100 nm,
- d) the aqueous polymer starting dispersions II have a monomodal distribution of the diameters of the starting polymer particles contained in them, which is such that if d x defines the diameter below which the particle diameter of X% by weight of all starting polymer particles present in the respective aqueous starting dispersion II the quotient (d 90 -d 10 ) / d 50 has a value of 0.1 to 0.6,
- e) between the volume V i obtainable by dividing the mass of the i th starting polymer II contained in the i th aqueous polymer starting dispersion II by the mass density of the i th starting polymer II and the correspondingly determined volume V j , provided that that both the weight-average particle diameter of the starting polymer particles contained in the i-th aqueous polymer starting dispersion II (
- f) between the total average of all aqueous polymer starting dispersions II which have a weight-average particle diameter of the starting polymer particles contained in them in the range from> 0 to ≦ 100 nm, the weight-average particle diameter of the latter Total amount of starting polymer particles contained (
- V i =
- Mass of the starting polymer contained in the i-th aqueous polymer starting dispersion II divided by its mass density,
- V ≦ 100 =
- Mass of the starting polymer contained in the total amount of all aqueous polymer starting dispersions II which have a weight-average particle diameter of the starting polymer particles contained in them in the range from> 0 to ≦ 100 nm, divided by their mass density,
- g) V ≦ 100 , based on the sum of all V i , is 0.3 to 10% by volume and
- h) the difference between the smallest and the largest weight-average particle diameter
- C) the total amount of the at least one aqueous polymer starting dispersion I to be added is placed in the polymerization vessel before the start of the radical aqueous emulsion polymerization, and
- D) the free-radical aqueous emulsion polymerization of the at least one free-radically polymerizable monomer by the feed process with the proviso that
- from the beginning of the free-radical aqueous emulsion polymerization, the at least one free-radically polymerizable monomer is fed into the polymerization vessel in such a way that at any time during the addition, the polymerization conversion of the monomers already previously supplied to the polymerization vessel is at least 80 mol% and
- the amount of dispersant present in the polymerization vessel at any time from the start of the free-radical aqueous emulsion polymerization, based on the sum of the masses of starting polymer I and monomers to be polymerized, which have already been fed to the polymerization vessel, is 0.5 to 5% by weight.
Weiterhin betrifft die vorliegende Erfindung das Verfahren zur Herstellung solcher wäßriger Polymerisatenddispersionen sowie ihre Verwendung als Bindemittel und als Massen zur Herstellung von Beschichtungen und Verklebungen.The present invention further relates to the process for the preparation of such aqueous polymer dispersions and their use as binders and as compositions for the production of coatings and bonds.
Wäßrige Polymerisatdispersionen sind Systeme, die als disperse Phase in einem wäßrigen Dispersionsmedium dispers verteilte Polymerisatteilchen enthalten.Aqueous polymer dispersions are systems which contain polymer particles dispersed as a disperse phase in an aqueous dispersion medium.
Ebenso wie Polymerisatlösungen beim Verdampfen des Lösungsmittels, weisen wäßrige Polymerisatdispersionen beim Verdampfen des wäßrigen Dispersionsmediums die Eigenschaft auf, Polymerisatfilme zu bilden, weshalb wäßrige Polymerisatdispersionen in vielfacher Weise als Bindemittel, z.B. für Anstrichfarben oder für Massen zum Beschichten von Leder, Anwendung finden.Just like polymer solutions when the solvent is evaporated, aqueous polymer dispersions have the property of forming polymer films when the aqueous dispersion medium is evaporated, which is why aqueous polymer dispersions are used in many ways as binders, for example for paints or for coating leather.
Wäßrige Polymerisatdispersionen mit hohem Polymerisatanteil sind insofern von besonderem Vorteil, als einerseits ihr relativ geringerer Anteil an wäßrigem Dispersionsmedium den Aufwand für das Verdampfen desselben, z.B. zur Filmbildung oder zur Herstellung von Polymerpulvern, reduziert und andererseits der Wertstoff Polymerisat in Anwendung einer relativ geringeren Menge wäßriger Phase als Trägermedium gelagert und transportiert werden kann.Aqueous polymer dispersions with a high proportion of polymer are particularly advantageous in that, on the one hand, their relatively lower proportion of aqueous dispersion medium means the expense of evaporating the same, e.g. for film formation or for the production of polymer powders, and on the other hand the polymer can be stored and transported in a relatively smaller amount of aqueous phase as the carrier medium.
Von Nachteil ist jedoch, daß mit zunehmender Volumenkonzentration (US-A 4,130,523) des Polymerisats die Herstellung wäßriger Polymerisatdispersionen problembehaftet ist. So nimmt einerseits der Fließwiderstand (die Viskosität) zu und erschwert sowohl die Abführung der Reaktionswärme als auch die Verarbeitung der wäßrigen Dispersion und andererseits wächst die Neigung der dispergierten Polymerisatteilchen sich aus Gründen der thermodynamischen Stabilität zusammenzulagern. Die dabei entstehenden Ausflockungen [a) Mikroflockungen oder Stippen; sie können durch herkömmliche Filtration in der Regel nicht abgetrennt werden; b) Makroflockungen oder Koagulat; ist normalerweise durch übliche Filtration abtrennbar;] führen insbesondere zu Störungen in den Verfilmungen der wäßrigen Polymerisatdispersionen und sind daher in der Regel unerwünscht.It is disadvantageous, however, that as the volume concentration (US Pat. No. 4,130,523) of the polymer increases, the preparation of aqueous polymer dispersions is problematic. Thus, on the one hand, the flow resistance (the viscosity) increases and complicates both the removal of the heat of reaction and the processing of the aqueous dispersion and, on the other hand, the tendency of the dispersed polymer particles to aggregate for reasons of thermodynamic stability. The resulting flocculation [a) micro-flakes or specks; they cannot usually be separated by conventional filtration; b) macro flakes or coagulum; can normally be separated off by conventional filtration;] lead in particular to disturbances in the filming of the aqueous polymer dispersions and are therefore generally undesirable.
Nach Untersuchungen über den Fließwiderstand wäßriger Polymerisatdispersionen weisen solche mit einer breiten Größenverteilung (polydispers) der dispergierten Polymerisatteilchen bei gleichem Feststoffgehalt in der Regel einen geringeren Fließwiderstand auf als solche mit einer engen Größenverteilung (im Grenzfall monodispers). Ferner zeigen grobteilige wäßrige Polymerisatdispersionen unter der Prämisse gleichen Feststoffgehalts einen geringeren Fließwiderstand als feinteilige wäßrige Polymerisatdispersionen.According to studies on the flow resistance of aqueous polymer dispersions, those with a broad size distribution (polydisperse) of the dispersed polymer particles with the same solids content generally have a lower flow resistance than those with a narrow size distribution (in the borderline case monodisperse). Furthermore, coarse-particle aqueous polymer dispersions show a lower flow resistance under the premise of the same solids content than fine-particle aqueous polymer dispersions.
Aus der EP-A 129 699 ist ein Verfahren zur Herstellung einer wäßrigen Polymerisatdispersion bekannt, bei dem man in einem Polymerisationsgefäß nach dem Verfahren der radikalischen wäßrigen Emulsionspolymerisation ungesättigte Monomere in an sich bekannter Weise polymerisiert und dabei eine wäßrige Dispersion eines Ausgangspolymerisats zusetzt, wobei der Zusatz der wäßrigen Dispersion des Ausgangspolymerisats abgeschlossen sein muß, bevor 40 Gew.-% der insgesamt zu polymerisierenden Monomeren einpolymerisiert sind sowie frühestens dann erfolgen darf, wenn die mittlere Teilchengröße des bei der Polymerisation der Monomeren entstehenden Emulsionspolymerisats den zweifachen Wert der mittleren Teilchengröße der wäßrigen Dispersion des Ausgangspolymerisats aufweist. Vorzugsweise wird dabei die wäßrige Dispersion des Ausgangspolymerisats nicht über einen längeren Zeitraum, sondern auf einmal zugegeben.From EP-A 129 699 a process for the preparation of an aqueous polymer dispersion is known, in which unsaturated monomers are polymerized in a polymerization vessel in accordance with the free-radical aqueous emulsion polymerization process in a manner known per se and an aqueous dispersion of a starting polymer is added, the addition the aqueous dispersion of the starting polymer must be completed before 40% by weight of the total to be polymerized Monomers are polymerized in and may only be carried out at the earliest if the average particle size of the emulsion polymer formed during the polymerization of the monomers has twice the value of the average particle size of the aqueous dispersion of the starting polymer. The aqueous dispersion of the starting polymer is preferably not added over a long period of time, but rather all at once.
Nachteilig an den so erhältlichen wäßrigen Polymerisatdispersionen ist, daß ihr Fließwiderstand oberhalb einer Feststoffvolumenkonzentration von 50 Vol.-% nicht voll zu befriedigen vermag und gemäß den Ausführungsbeispielen die Feststoffvolumenkonzentration auf Werte unter 65 Vol.-% beschränkt ist.A disadvantage of the aqueous polymer dispersions obtainable in this way is that their flow resistance above a solid volume concentration of 50% by volume is not fully satisfactory and, according to the exemplary embodiments, the solid volume concentration is limited to values below 65% by volume.
Die US-A 4,130,523 betrifft ein Verfahren zur Herstellung wäßriger Polymerisatdispersionen, bei dem während des Polymerisationsprozesses laufend bereits gebildete wäßrige Polymerisatdispersion aus der Reaktionszone entfernt, gelagert und später der Reaktionszone als eine Art Ausgangspolymerisatdispersion wieder zugeführt wird. Nachteilig an diesem Verfahren ist, daß es für eine großtechnische Realisierung ungeeignet ist.US Pat. No. 4,130,523 relates to a process for the preparation of aqueous polymer dispersions, in which aqueous polymer dispersions which have already formed during the polymerization process are removed from the reaction zone, stored and later fed back to the reaction zone as a type of starting polymer dispersion. A disadvantage of this process is that it is unsuitable for large-scale implementation.
Die US-A 3,424,706 bezieht sich auf ein Verfahren zur Herstellung wäßriger Polymerisatdisperionen, deren Polymerisate wenigstens 70 bis 97 Gew.-% Vinylidenchlorid einpolymerisiert enthalten, bei dem die Polymerisation der Monomeren unter Zusatz einer wäßrigen Dispersion eines Ausgangspolymerisats erfolgt. Unter anderem enthält die US-A 3,424,706 den Hinweis, die zu polymerisierenden Monomeren und die wäßrige Dispersion des Ausgangspolymerisats miteinander zu vermischen und dieses Gemisch der einen Teil des Polymerisationsansatzes umfassenden Vorlage zuzuführen.US Pat. No. 3,424,706 relates to a process for the preparation of aqueous polymer dispersions, the polymers of which contain at least 70 to 97% by weight of copolymerized vinylidene chloride, in which the polymerization of the monomers takes place with the addition of an aqueous dispersion of a starting polymer. Among other things, US Pat. No. 3,424,706 contains the information to mix the monomers to be polymerized and the aqueous dispersion of the starting polymer with one another and to feed this mixture to the template comprising part of the polymerization batch.
Nachteilig an diesem Verfahren ist, daß es auf Monomerengemische beschränkt ist, die hauptsächlich Vinylidenchlorid enthalten. Darüber hinaus vermag gemäß den Ausfuhrungsbeispielen auch bei den nach diesem Verfahren erhältlichen wäßrigen Polymerisatdispersionen sowohl der Fließwiderstand oberhalb einer Feststoffvolumenkonzentration von 50 Vol.-%, als auch die in noch befriedigend fließfähigem Zustand erreichbare Obergrenze der Feststoffvolumenkonzentration nicht zu befriedigen.A disadvantage of this process is that it is limited to monomer mixtures which mainly contain vinylidene chloride. In addition, according to the exemplary embodiments, the flow resistance above a solids volume concentration of 50% by volume, as well as that which can still be achieved in a satisfactorily flowable state, can also be achieved with the aqueous polymer dispersions obtainable by this process Unsatisfactory upper limit of the solid volume concentration.
Ziel der vorliegenden Erfindung war daher, wäßrige Polymerisatdispersionen zur Verfügung zu stellen, die in einfacher, großtechnisch geeigneter, reproduzierbarer und nicht auf spezielle Monomere beschränkter Weise bei erhöhter Feststoffvolumenkonzentration mit reduziertem Fließwiderstand sowie reduziertem Gehalt an Ausflockungen erhältlich sind.The aim of the present invention was therefore to provide aqueous polymer dispersions which are obtainable in a simple, industrially suitable, reproducible and not limited to special monomers manner with an increased solid volume concentration with reduced flow resistance and reduced flocculation content.
Demgemäß wurden die eingangs definierten wäßrigen Polymerisatenddispersionen gefunden.Accordingly, the aqueous polymer dispersions defined at the outset were found.
Bemerkenswerterweise ist der erfindungsgemäße Gegenstand nicht auf die radikalische wäßrige Emulsionspolymerisation von hauptsächlich oder ausschließlich aus Vinyl- und/oder Vinylidenhalogeniden zusammengesetzten Monomerengemischen beschränkt, ist doch allgemein bekannt, daß die Entwicklung der dispersen Phase im Fall von Vinyl- und/oder Vinylidenhalogeniden verschiedenen Monomeren ein wesentlich komplexeres Erscheinigungsbild aufweist.Remarkably, the subject matter of the invention is not limited to the free radical aqueous emulsion polymerization of monomer mixtures composed mainly or exclusively of vinyl and / or vinylidene halides, since it is generally known that the development of the disperse phase in the case of vinyl and / or vinylidene halides different monomers is essential has a more complex appearance.
Für das erfindungsgemäße Verfahren kommen daher als radikalisch polymerisierbare Monomere unter anderen insbesondere monoethylenisch ungesättigte Monomere wie Olefine, z.B. Ethylen, vinylaromatische Monomere wie Styrol, α-Methylstyrol, o-Chlorstyrol oder Vinyltoluole, Ester aus Vinylalkohol und 1 bis 18 C-Atome aufweisenden Monocarbonsäuren wie Vinylacetat, Vinylpropionat, Vinyl-n-butyrat, Vinyllaurat und Vinylstearat, Ester aus vorzugsweise 3 bis 6 C-Atome aufweisenden α,β-monoethylenisch ungesättigten Mono- und Dicarbonsäuren, wie insbesondere Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure und Itaconsäure, mit im allgemeinen 1 bis 12, vorzugsweise 1 bis 8 und insbesondere 1 bis 4 C-Atome aufweisenden Alkanolen wie besonders Acrylsäure- und Methyacrylsäuremethyl-, -ethyl, -n-butyl, -iso-butyl und -2-ethylhexylester, Maleinsäuredimethylester oder Maleinsäure-n-butylester, Nitrile α,β-monoethylenisch ungesättigter Carbonsauren wie Acrylnitril sowie C4-8-konjugierte Diene wie 1,3-Butadien und Isopren in Betracht. Die genannten Monomeren bilden in der Regel die Hauptmonomeren, die, bezogen auf die Gesamtmenge der nach dem Verfahren der radikalischen wäßrigen Emulsionspolymerisation zu polymerisierenden Monomeren, normalerweise einen Anteil von mehr als 50 Gew.-% auf sich vereinen. Monomere, die für sich polymerisiert üblicherweise Homopolymerisate ergeben, die eine erhöhte Wasserlöslichkeit aufweisen, werden im Normalfall lediglich als modifizierende Monomere in Mengen, bezogen auf die Gesamtmenge der zu polymerisierenden Monomeren, von weniger als 50 Gew.-%, in der Regel 0,5 bis 20, vorzugsweise 1 bis 10 Gew.-%, miteinpolymerisiert.For the process according to the invention, therefore, the radically polymerizable monomers used include, in particular, monoethylenically unsaturated monomers such as olefins, for example ethylene, vinylaromatic monomers such as styrene, α-methylstyrene, o-chlorostyrene or vinyltoluenes, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms, such as Vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of α, β-monoethylenically unsaturated mono- and dicarboxylic acids, preferably having 3 to 6 carbon atoms, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with in general 1 to 12, preferably 1 to 8 and in particular 1 to 4, alkanols, such as, in particular, methyl, ethyl, n-butyl, isobutyl and -2-ethylhexyl acrylate, dimethyl maleate or n-maleate, especially acrylic acid and methacrylic acid. butyl esters, nitriles α, β-monoethylenically unsaturated carboxylic acids such as acrylonitrile and C 4-8 conjugate dienes such as 1,3-butadiene and isoprene. The monomers mentioned generally form the main monomers which, based on the total amount of the monomers to be polymerized by the free-radical aqueous emulsion polymerization process, normally account for more than 50% by weight. Monomers which, when polymerized on their own, usually give homopolymers which have an increased solubility in water, are normally only used as modifying monomers in amounts, based on the total amount of the monomers to be polymerized, of less than 50% by weight, generally 0.5 up to 20, preferably 1 to 10 wt .-%, co-polymerized.
Beispiele für derartige Monomere sind 3 bis 6 C-Atome aufweisende α,β-monoethylenisch ungesättigte Mono- und Dicarbonsäuren und deren Amide wie z.B. Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Itaconsäure, Acrylamid und Methacrylamid, ferner Vinylsulfonsäure und deren wasserlösliche Salze sowie N-Vinylpyrrolidon. Monomere, die üblicherweise die innere Festigkeit der Verfilmungen der wäßrigen Polymerisatenddispersion erhöhen, werden in der Regel ebenfalls nur in untergeordneten Mengen, meist 0,5 bis 10 Gew.-% bezogen auf die Gesamtmenge der zu polymerisierenden Monomeren, miteinpolymerisiert. Normalerweise weisen derartige Monomere eine Epoxy-, Hydroxy-, N-Methylol-, Carbonyl- oder wenigstens zwei nicht konjugierte ethylenisch ungesättigte Doppelbindungen auf. Beispiele hierfür sind N-Alkylolamide von 3 bis 10 C-Atome aufweisenden α,β-monoethylenisch ungesättigten Carbonsäuren sowie deren Ester mit 1 bis 4 C-Atome aufweisenden Alkoholen, unter denen das N-Methylolacrylamid und das N-Methylolmethacrylamid ganz besonders bevorzugt sind, zwei Vinylreste aufweisende Monomere, zwei Vinylidenreste aufweisende Monomere sowie zwei Alkenylreste aufweisende Monomere. Besonders geeignet sind dabei die Di-Ester zweiwertiger Alkohole mit α,β-monoethylenisch ungesättigten Monocarbonsäuren unter denen wiederum die Acryl- und Methacrylsäure vorzugsweise eingesetzt werden. Beispiele für derartige zwei nicht konjugierte ethylenisch ungesättigte Doppelbindungen aufweisende Monomere sind Alkylenglycoldiacrylate- und dimethacrylate wie Ethylenglycoldiacrylat, 1,3-Butylenglycoldiacrylat, 1,4-Butylenglycoldiacrylat sowie Propylenglycoldiacrylat, Divinylbenzol, Vinylmethacrylat, Vinylacrylat, Allylmethacrylat, Allylacrylat, Diallylmaleat, Diallylfumarat, Methylenbisacrylamid, Cyclopentadienylacrylat oder Triallylcyanurat. In diesem Zusammenhang von besonderer Beeutung sind auch die Methacrylsäure- und Acrylsäure-C1-C8-Hydroxyalkylester wie n-Hydroxyethyl-, n-Hydroxypropyl- oder n-Hydroxybutylacrylat und -methacrylat sowie Verbindungen wie Diacetonacrylamid und Acetylacetoxyethylacrylat bzw. -methacrylat. Neben ungesättigte Doppelbindungen aufweisenden Monomeren können in untergeordneten Mengen, üblicherweise 0,01 bis 2 Gew.-% bezogen auf die zu polymerisierenden Monomeren, das Molekulargewicht regelnde Substanzen wie tert.-Dodecylmercaptan sowie 3-Mercaptopropyltrimethoxysilan miteinpolymerisiert werden. Vorzugsweise werden derartige Substanzen im Gemisch mit den zu polymerisierenden Monomeren der Polymerisationszone zugegeben.Examples of such monomers are α, β-monoethylenically unsaturated mono- and dicarboxylic acids and their amides such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamide and methacrylamide, also vinyl sulfonic acid and its water-soluble salts and N- Vinyl pyrrolidone. Monomers, which usually increase the internal strength of the films in the aqueous polymer dispersion, are generally also copolymerized only in minor amounts, usually 0.5 to 10% by weight, based on the total amount of the monomers to be polymerized. Such monomers normally have an epoxy, hydroxy, N-methylol, carbonyl or at least two non-conjugated ethylenically unsaturated double bonds. Examples of these are N-alkylolamides of α, β-monoethylenically unsaturated carboxylic acids having 3 to 10 C atoms and their esters with alcohols having 1 to 4 C atoms, among which the N-methylolacrylamide and the N-methylolmethacrylamide are very particularly preferred, two monomers having vinyl radicals, two monomers having vinylidene radicals and two monomers having alkenyl radicals. The di-esters of dihydric alcohols with α, β-monoethylenically unsaturated monocarboxylic acids are particularly suitable, among which in turn acrylic and methacrylic acid are preferably used. Examples of such monomers having two non-conjugated ethylenically unsaturated double bonds are alkylene glycol diacrylate and dimethacrylates such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and propylene glycol diacrylate, divinylbenzene, vinyl methacrylate, allyl acrylate, allyl acrylate, vinyl acrylate or triallyl cyanurate. Of particular importance in this context are the methacrylic acid and acrylic acid-C 1 -C 8 -hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-Hydroxybutyl acrylate and methacrylate and compounds such as diacetone acrylamide and acetylacetoxyethyl acrylate or methacrylate. In addition to monomers having unsaturated double bonds, minor amounts, usually 0.01 to 2% by weight, based on the monomers to be polymerized, of copolymerizing substances such as tert-dodecyl mercaptan and 3-mercaptopropyltrimethoxysilane can also be copolymerized. Such substances are preferably added to the polymerization zone in a mixture with the monomers to be polymerized.
Als Dispergiermittel kommen sowohl die zur Durchführung von radikalischen wäßrigen Emulsionspolymerisationen üblicherweise eingesetzten Schutzkolloide als auch Emulgatoren in Betracht. Geeignete Schutzkolloide sind beispielsweise Polyvinylalkohole, Cellulosederivate oder Vinylpyrrolidon enthaltende Copolymerisate. Eine ausführliche Beschreibung weiterer geeigneter Schutzkolloide findet sich in Houben-Weyl, Methoden der organischen Chemie, Band XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, S. 411 bis 420. Selbstverständlich können auch Gemische aus Emulgatoren und/oder Schutzkolloiden verwendet werden. Vorzugsweise werden als Dispergiermittel ausschließlich Emulgatoren eingesetzt, deren relative Molekulargewichte im Unterschied zu den Schutzkolloiden üblicherweise unter 1000 liegen. Sie können sowohl anionischer, kationischer oder nichtionischer Natur sein. Selbstverständlich müssen im Falle der Verwendung von Gemischen grenzflächenaktiver Substanzen die Einzelkomponenten miteinander verträglich sein, was im Zweifelsfall an Hand weniger Vorversuche überprüft werden kann. Im allgemeinen sind anionische Emulgatoren untereinander und mit nicht-ionischen Emulgatoren verträglich. Desgleichen gilt auch für kationische Emulgatoren, während anionische und kationische Emulgatoren meistens miteinander unverträglich sind. Gebräuchliche Emulgatoren sind z.B. ethoxylierte Mono-, Di- und Tri-Alkylphenole (EO-Grad: 3 bis 50, Alkylrest: C4 bis C9), ethoxylierte Fettalkohole (EO-Grad: 3 bis 50, Alkylrest: C8 bis C36), sowie Alkali- und Ammoniumsalze von Alkylsulfaten (Alkylrest: C8 bis C12), von Schwefelsäurehalbestern ethoxylierter Alkanole (EO-Grad: 4 bis 30, Alkylrest: C12 bis C18) und ethoxylierter Alkylphenole (EO-Grad: 3 bis 50, Alkylrest: C4 bis C9), von Alkylsulfonsäuren (Alkylrest: C12 bis C18) und von Alkylarylsulfonsäuren (Alkylrest: C9 bis C18). Weitere geeignete Emulgatoren finden sich in Houben-Weyl, Methoden der organischen Chemie, Band XIV/1, Makromolekulare Stoffe, Georg-Thieme Verlag, Stuttgart, 1961, Seiten 192 bis 208.Suitable dispersants are both the protective colloids usually used to carry out free-radical aqueous emulsion polymerizations and emulsifiers. Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or copolymers containing vinyl pyrrolidone. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411 to 420. Of course, mixtures of emulsifiers and / or protective colloids can be used. Preferably only emulsifiers are used as dispersants, the relative molecular weights of which, in contrast to the protective colloids, are usually below 1000. They can be anionic, cationic or nonionic in nature. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked with a few preliminary tests if in doubt. In general, anionic emulsifiers are compatible with one another and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with one another. Common emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C 4 to C 9 ), ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C 8 to C 36 ), as well as alkali and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C 12 to C 18 ) and ethoxylated alkyl phenols (EO degree: 3 to 50, alkyl radical: C 4 to C 9 ), of alkyl sulfonic acids (alkyl radical: C 12 to C 18 ) and of alkylarylsulfonic acids (alkyl radical: C 9 to C 18 ). Further suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme Verlag, Stuttgart, 1961, pages 192 to 208.
Als besonders geeignete grenzflächenaktive Substanzen haben sich Verbindungen der allgemeinen Formel I
Als radikalische Polymerisationsinitiatoren kommen alle diejenigen in Betracht, die in der Lage sind, eine radikalische wäßrige Emulsionspolymerisation auszulösen. Es kann sich dabei sowohl um Peroxide, z.B. Alkalimetallperoxidisulfate, als auch um Azoverbindungen handeln. Vorzugsweise werden kombinierte Systeme, die aus wenigstens einem organischen Reduktionsmittel und wenigstens einem Peroxid und/oder Hydroperoxid zusammengesetzt sind, z.B. tert.-Butylhydroperoxid und das Natriummetallsalz der Hydroxymethansulfinsäure oder Wasserstoffperoxid und Ascorbinsäure, und ganz besonders bevorzugt kombinierte Systeme, die darüber hinaus eine geringe Menge einer im Polymerisationsmedium löslichen Metallverbindung, deren metallische Komponente in mehreren Wertigkeitsstufen auftreten kann, enthalten, z.B. Ascorbinsäure/Eisen(II)sulfat/Wasserstoffperoxid, eingesetzt, wobei anstelle von Ascorbinsäure auch häufig das Natriummetallsalz der Hydroxymethansulfinsäure, Natriumsulfit, Natriumhydrogensulfit oder Natriummetalldisulfit und anstelle von Wasserstoffperoxid tert. Butylhydroperoxid oder Alkalimetallperoxidisulfate und/oder Ammoniumperoxidisulfat angewendet werden. Anstelle eines wasserlöslichen Eisen (II)-salzes wird häufig eine Kombination aus wasserlöslichen Fe/V-Salzen benutzt. Vorzugsweise beträgt die Menge der eingesetzten radikalischen Initiatorsysteme, bezogen auf die Gesamtmenge der zu polymerisierenden Monomeren, 0,1 bis 2 Gew.-%.Free radical polymerization initiators are all those which are capable of initiating a free radical aqueous emulsion polymerization. It can be both peroxides, for example alkali metal peroxydisulfates, as well as azo compounds. Combined systems which are composed of at least one organic reducing agent and at least one peroxide and / or hydroperoxide, for example tert.-butyl hydroperoxide and the sodium metal salt of hydroxymethanesulfinic acid or hydrogen peroxide and ascorbic acid, and very particularly preferred combined systems which are moreover a small amount contain a metal compound soluble in the polymerization medium, the metallic component of which can occur in several valence stages, for example ascorbic acid / iron (II) sulfate / hydrogen peroxide, the sodium metal salt of hydroxymethanesulfinic acid, sodium sulfite, sodium hydrogen sulfite or sodium metal disulfite and instead of hydrogen peroxide also frequently being used instead of ascorbic acid tert. Butyl hydroperoxide or alkali metal peroxydisulfates and / or ammonium peroxydisulfate can be used. Instead of a water-soluble iron (II) salt, a combination of water-soluble Fe / V salts is often used. The amount of free-radical initiator systems used is preferably 0.1 to 2% by weight, based on the total amount of the monomers to be polymerized.
Die Art und Weise, in der das radikalische Initiatorsystem im Verlauf der erfindungsgemäßen radikalischen wäßrigen Emulsionspolymerisation dem Polymerisationsgefäß zugegeben wird, ist hinsichtlich des Erfolgs des erfindungsgemäßen Verfahrens eher von untergeordneter Bedeutung. Das Initiatorsystem kann sowohl vollständig in das Polymerisationsgefäß vorgelegt, als auch nach Maßgabe seines Verbrauchs im Verlauf der radikalischen wäßrigen Emulsionspolymerisation kontinuierlich oder stufenweise zugesetzt werden. Im einzelnen hängt dies in an sich dem Durchschnittsfachmann bekannter Weise sowohl von der chemischen Natur des Initiatorsystems als auch von der Polymerisationstemperatur ab.The manner in which the free-radical initiator system is added to the polymerization vessel in the course of the free-radical aqueous emulsion polymerization according to the invention is of minor importance with regard to the success of the process according to the invention. The initiator system can either be completely introduced into the polymerization vessel or, depending on its consumption, can be added continuously or in stages in the course of the free-radical aqueous emulsion polymerization. Specifically, this depends on the chemical nature of the initiator system and on the polymerization temperature in a manner known per se to the person skilled in the art.
Polymerisationsdruck und Polymerisationstemperatur sind gleichfalls von eher untergeordneter Bedeutung. Im allgemeinen arbeitet man bei Temperaturen zwischen Raumtemperatur und 100°C, vorzugsweise bei Temperaturen von 50 bis 95°C. Die Anwendung von erhöhtem oder vermindertem Druck ist möglich, so daß die Polymerisationstemperatur auch 100°C überschreiten und bis zu 130°C betragen kann. Vorzugsweise werden leichtflüchtige Monomere wie Ethylen, Butadien oder Vinylchlorid unter erhöhtem Druck polymerisiert. Zur pH-Wert Regulierung des Polymerisationsmediums kann während der erfindungsgemäßen radikalischen wäßrigen Emulsionspolymerisation beispielsweise Ammoniak zugegeben werden.Polymerization pressure and polymerization temperature are also of minor importance. In general, temperatures between room temperature and 100 ° C, preferably at temperatures of 50 to 95 ° C. The application of increased or reduced pressure is possible, so that the polymerization temperature also exceed 100 ° C and can be up to 130 ° C. Volatile monomers such as ethylene, butadiene or vinyl chloride are preferably polymerized under elevated pressure. To regulate the pH of the polymerization medium, ammonia, for example, can be added during the free radical aqueous emulsion polymerization according to the invention.
Die für die erfindungsgemäße radikalische wäßrige Emulsionspolymerisation beispielhaft als geeignet genannten radikalisch polymerisierbaren Monomeren eignen sich nicht nur als Konstituenten des erfindungsgemäß zu polymerisierenden Monomerengemisches. Vielmehr eignen sie sich in gleicher Weise wie die für die erfindungsgemäße radikalische wäßrige Emulsionspolymerisation empfohlenen Polymerisationsinitiatoren, das Molekulargewicht regelnden Verbindungen und den pH-Wert regulierenden Mittel auch als Konstituenten der Ausgangspolymerisate I, II, bzw. der diese enthaltenden Polymerisatausgangsdispersionen, wobei die Monomeren-, Regler- und Initiatorenzusammensetzung zur Herstellung der wäßrigen Polymerisatausgangsdispersionen I, II mit derjenigen für das erfindungsgemäße Verfahren sowohl deckungsgleich als auch verschieden sein kann. Die ebenda gemachten Aussagen gelten im übertragenen Sinn auch für die zur Herstellung der wäßrigen Polymerisatausgangsdispersionen I, II einzusetzenden grenzflächenaktiven Substanzen.The free-radically polymerizable monomers mentioned as suitable for the free radical aqueous emulsion polymerization according to the invention are suitable not only as constituents of the monomer mixture to be polymerized according to the invention. Rather, they are suitable in the same way as the polymerization initiators recommended for the radical aqueous emulsion polymerization according to the invention, the compounds regulating the molecular weight and the pH-regulating agents, also as constituents of the starting polymers I, II or the starting polymer dispersions containing them, the monomers, Controller and initiator composition for the preparation of the aqueous polymer starting dispersions I, II with which those for the process according to the invention can be congruent as well as different. The statements made here also apply in a figurative sense to the surface-active substances to be used for the preparation of the aqueous polymer starting dispersions I, II.
Wäßrige Polymerisatausgangsdispersionen I sind in einfacher Weise dadurch erhältlich, daß man in definitionsgemäßer Weise n wäßrige Polymerisatausgangsdispersionen II, deren Teilchendurchmesserverteilungsfunktionen vorzugsweise im wesentlichen nicht überlappen, zusammengibt. Anwendungstechnisch bevorzugt liegt n im Bereich 2 bis 10, vorzugsweise im Bereich 2 bis 5. Die Herstellung wäßriger Polymerisatausgangsdispersionen II ist an sich bekannt. Entsprechende Lehren sind z. B. in Houben-Weyl, Methoden der organischen Chemie, Band E 20, Teil I, Makromolekulare Stoffe, Georg-Thieme Verlag, Stuttgart, 1987, Seiten 248 bis 268 zu finden. Bei einem vorzugsweise angewendeten Feststoffgehalt von 20 bis 40 Gew.-% und einem angestrebten gewichtsmittleren Teildurchmesser von > 0 bis ≦ 50 nm, sind die wäßrigen Polymerisatausgangsdispersionen II in besonders einfacher Weise z. B. dadurch erhältlich, daß man die wäßrige Phase, die Monomeren, die radikalischen Initiatoren (normalerweise 0,1 bis 5 Gew.-%, bezogen auf die Menge der zu polymerisierenden Ausgangsmonomeren) und Dispergiermittel (üblicherweise 10 bis 50 Gew.-%, bezogen auf die Menge der zu polymerisierenden Ausgangsmonomeren) bei niederer Temperatur miteinander vermischt und nach Vermischen auf die Polymerisationstemperatur erwärmt und polymerisiert (zunehmende Mengen an Dispergiermittel bedingen in der Regel einen abnehmenden gewichtsmittleren Teilchendurchmesser). Bei einer anderen Variante umfaßt die Vorlage im wesentlichen alle Komponenten, der Polymerisationsinitiator wird jedoch nach Erwärmen auf die Reaktionstemperatur unter Aufrechterhalten derselben kontinuierlich zugeführt. Hinsichtlich Polymerisationstemperatur und Druck gelten die bezüglich des erfindungsgemäßen Verfahrens gemachten Aussagen.Aqueous starting polymer dispersions I can be obtained in a simple manner by combining n aqueous starting polymer dispersions II, the particle diameter distribution functions of which preferably do not substantially overlap, in a manner defined by definition. From an application point of view, n is preferably in the range from 2 to 10, preferably in the range from 2 to 5. The preparation of aqueous polymer starting dispersions II is known per se. Appropriate teachings are e.g. B. in Houben-Weyl, Methods of Organic Chemistry, Volume E 20, Part I, Macromolecular Substances, Georg-Thieme Verlag, Stuttgart, 1987, pages 248 to 268. With a preferably used solids content of 20 to 40 wt .-% and a desired weight-average part diameter of> 0 to ≦ 50 nm, the aqueous polymer dispersion II are in a particularly simple manner, for. B. obtainable by the aqueous phase, the monomers, the free radical initiators (normally 0.1 to 5 wt .-%, based on the amount of the starting monomers to be polymerized) and dispersants (usually 10 to 50 wt .-%, based on the amount of starting monomers to be polymerized) mixed together at a low temperature and, after mixing, heated to the polymerization temperature and polymerized (increasing amounts of dispersant usually result in a decreasing weight average particle diameter). In another variant, the initial charge comprises essentially all of the components, but the polymerization initiator is fed continuously after heating to the reaction temperature while maintaining the same. With regard to the polymerization temperature and pressure, the statements made with regard to the process according to the invention apply.
Ausgehend von solchermaßen erhältlichen relativ feinteiligen wäßrigen Polymerisatausgangsdispersionen II sind grobteilige wäßrige Polymerisatausgangsdispersionen II beispielsweise dadurch erhältlich, daß man in einem Polymerisationsgefäß eine feinteilige wäßrige Polymerisatausgangsdispersion II vorlegt, auf die Polymerisationstemperatur erwärmt und anschließend weitere Monomere, üblicherweise in wäßrigem Medium voremulgiert, und Polymerisationsinitiator unter Aufrechterhalten der Polymerisationstemperatur ins Polymerisationsgefäß zuführt. Die im Rahmen der wäßrigen Monomerenemulsion zugeführte Menge Emulgiermittel wird dabei so bemessen, daß die in der resultierenden grobteiligeren wäßrigen Polymerisatausgangsdispersion II enthaltene Dispergiermittelgesamtmenge, bezogen auf das resultierende grobteilige Ausgangspolymerisat II, 0,5 bis 5, vorzugsweise 0,5 bis 3 Gew.-% beträgt. Die zu erzielende Teilchenvergröberung wird im wesentlichen durch das Mengenverhältnis von in der Vorlage enthaltenen feinteiligen Ausgangspolymerisat-II-teilchen und zugeführten Monomeren bestimmt. Selbstverständlich können der Prozeß der Herstellung einer relativ feinteiligen wäßrigen Polymerisatausgangsdispersion II und der Prozeß der Vergröberung nahtlos ineinander übergehen. Die Angaben über gewichtsmittlere Polymerisatteilchendurchmesser sowie Quotienten (d90-d10)/d50 der wäßrigen Polymerisatausgangsdispersionen beziehen sich hier stets auf Bestimmungen mittels der analytischen Ultrazentrifuge (W. Mächtle, Makromolekulare Chemie, Bd. 185 (1984), S. 1025-1039). Die Bestimmungen der Polymerisatteilchengrößenverteilung der wäßrigen Polymerisatenddispersionen wurden mit der sogenannten Coupling-PSD-Technik in der analytischen Ultrazentrifuge bestimmt (vgl. W. Mächtle, Angewandte Makromolekulare Chemie 162 (1988) 35-42 (Nr. 2735)).Starting from such relatively finely divided aqueous polymer starting dispersions II, which are obtainable in this way, coarse-particle aqueous polymer starting dispersions II can be obtained, for example, by placing a finely divided aqueous polymer starting dispersion II in a polymerization vessel, heating to the polymerization temperature and then further monomers, usually pre-emulsified in an aqueous medium, and maintaining the initiator Feeds the polymerization temperature into the polymerization vessel. The amount of emulsifier added in the context of the aqueous monomer emulsion is such that the total amount of dispersant contained in the resulting coarsely divided aqueous polymer starting dispersion II, based on the resulting coarse starting polymer II, 0.5 to 5, preferably 0.5 to 3% by weight. is. The particle coarsening to be achieved is essentially determined by the quantitative ratio of the finely divided starting polymer II particles contained in the initial charge and the monomers supplied. Of course, the process of producing a relatively finely divided aqueous polymer starting dispersion II and the process of coarsening can merge seamlessly. The information about weight-average polymer particle diameters and quotients (d 90 -d 10 ) / d 50 of the aqueous polymer starting dispersions always refer to determinations by means of the analytical ultracentrifuge (W. Mächtle, Makromolekulare Chemie, Vol. 185 (1984), pp. 1025-1039 ). The determinations of the polymer particle size distribution of the aqueous Final polymer dispersions were determined using the so-called coupling PSD technique in the analytical ultracentrifuge (cf. W. Mächtle, Angewandte Makromolekulare Chemie 162 (1988) 35-42 (No. 2735)).
Bevorzugt werden erfindungsgemäß solche wäßrigen Polymerisatausgangsdispersionen I eingesetzt, die an wäßrigen Polymerisatausgangsdispersionen II mit einem
Darüber hinaus werden vorzugsweise solche wäßrigen Polymerisatausgangsdispersionen I verwendet, für die alle k-Werte im Bereich 0,9 bis 1,1 und alle k'-Werte im Bereich 0,75 bis 3, vorzugsweise im Bereich 0,9 bis 1,5 liegen. Ganz besonders vorteilhaft ist es, wenn alle Werte k bzw. k' für die wenigstens eine verwendete wäßrige Polymerisatausgangsdispersion I etwa 1 betragen.In addition, those aqueous polymer starting dispersions I are preferably used for which all k values are in the range 0.9 to 1.1 and all k 'values are in the range 0.75 to 3, preferably in the range 0.9 to 1.5 . It is particularly advantageous if all values k and k 'for the at least one aqueous polymer starting dispersion I used are about 1.
Weiterhin beträgt V≦100 in der wenigstens einen zuzusetzenden wäßrigen Polymerisatausgangsdispersion I, bezogen auf die Summe aller in ihr enthaltenen Vi, mit Vorteil 0,5 bis 5 Vol.-%. Der Gehalt an Dispergiermittel in der wenigstens einem wäßrigen Polymerisatausgangsdispersion I beträgt normalerweise 0,5 bis 5 Gew.-%, bezogen auf die Menge des darin enthaltenen Ausgangspolymerisats I.Furthermore, V ≦ 100 in the at least one aqueous polymer starting dispersion I to be added, based on the sum of all V i contained therein, is advantageously 0.5 to 5% by volume. The content of dispersant in the at least one aqueous polymer starting dispersion I is normally 0.5 to 5% by weight, based on the amount of the starting polymer I contained therein.
Definitionsgemäß sind die erfindungsgemäßen wäßrigen Polymerisatenddispersionen dadurch erhältlich, daß man die Gesamtmenge der wenigstens einen zuzusetzenden wäßrigen Polymerisatausgangsdispersion I vor Beginn der erfindungsgemäßen radikalischen wäßrigen Emulsionspolymerisation ins Polymerisationsgefäß vorlegt und die radikalische wäßrige Emulsionspolymerisation des wenigstens einen radikalisch zu polymerisierenden Monomeren nach dem Zulaufverfahren durchführt.According to the definition, the aqueous polymer final dispersions according to the invention are obtainable by introducing the total amount of the at least one aqueous polymer starting dispersion I to be added into the polymerization vessel before the free-radical aqueous emulsion polymerization according to the invention is started and the free-radical aqueous emulsion polymerization of the at least one monomer to be radically polymerized by the feed process.
Werden Polymerisatenddispersionen mit besonders hoher Feststoffvolumenkonzentration angestrebt, ist es zweckmäßig die Monomeren dem Polymerisationsgefäß für sich zuzuführen. Ansonsten werden die radikalisch zu polymerisierenden Monomeren vorzugsweise in wäßriger Phase voremulgiert zugeführt, wobei die Menge des diesbezüglich verwendeten Emulgators, bezogen auf die Menge der emulgierten Monomeren, mit Vorteil 0,5 bis 3 Gew.-% beträgt.If final polymer dispersions with a particularly high solid volume concentration are desired, it is expedient to feed the monomers to the polymerization vessel on their own. Otherwise, the monomers to be polymerized by free radicals are preferably supplied pre-emulsified in the aqueous phase, the amount of the emulsifier used in this regard, based on the amount of the emulsified monomers, advantageously being 0.5 to 3% by weight.
In anwendungstechnisch zweckmäßiger Weise wird man neben der wenigstens einen zuzusetzenden wäßrigen Polymerisatausgangsdispersion I etwas Polymerisationsinitiator und einen geringen Teil des wenigstens einen zu polymerisierenden Monomeren (bezogen auf dessen Gesamtmenge in typischer Weise 1 bis 5 Gew.-%) ins Polymerisationsgefäß vorlegen, das Gemisch auf die Polymerisationstemperatur erhitzen und anschließend unter Aufrechterhaltung der Polymerisation die restlichen Monomeren und weiteren Polymerisationsinitiator dem Polymerisationsgefäß synchron so zulaufen lassen, daß ab Beginn der radikalischen wäßrigen Emulsionspolymerisation der Zulauf des wenigstens einen radikalisch polymerisierbarer Monomeren ins Polymerisationsgefäß so erfolgt, daß zu jedem Zeitpunkt des Zulaufs der Polymerisationsumsatz der bereits zuvor dem Polymerisationsgefäß insgesamt zugeführten Monomeren wenigstens 80, vorzugsweise wenigstens 90 mol.-% beträgt, wobei sich die Initiatorzufuhr vorzugsweise etwas über die Dauer der Monomerenzufuhr hinaus erstreckt. Die erfindungsgemäße radikalische wäßrige Emulsionspolymerisation kann aber auch so geführt werden, daß die Vorlage nur die wäßrige Polymerisatausgangsdispersion I enthält, auf die Polymerisationstemperatur erwärmt wird und anschließend Polymerisationsinitiator- und Monomerenzulauf gleichzeitig beginnend die Polymerisation auslösen. Natürlich kann im Verlauf des Zulaufsverfahrens dem Polymerisationsgefäß zusätzliches Dispergiermittel, z. B. räumlich getrennt oder als Bestandteil der Monomerenemulsion, zugeführt werden.In terms of application technology, in addition to the at least one aqueous polymer starting dispersion I to be added, some polymerization initiator and a small part of the at least one monomer to be polymerized (based on its total amount typically 1 to 5% by weight) are placed in the polymerization vessel, the mixture onto which Heat the polymerization temperature and then, while maintaining the polymerization, allow the remaining monomers and further polymerization initiator to run synchronously into the polymerization vessel in such a way that from the start of the free-radical aqueous emulsion polymerization the at least one free-radically polymerizable monomer is fed into the polymerization vessel in such a way that the polymerization conversion occurs at any time during the addition The total amount of monomers supplied to the polymerization vessel beforehand is at least 80, preferably at least 90, mol%, the initiator feed preferably being extends somewhat beyond the duration of the monomer feed. However, the radical aqueous emulsion polymerization according to the invention can also be carried out in such a way that the initial charge contains only the aqueous polymer starting dispersion I, is heated to the polymerization temperature and then initiates the polymerization initiator and monomer feed simultaneously starting the polymerization. Of course, additional dispersing agent, e.g. B. spatially separated or as part of the monomer emulsion.
Falls dies der Fall ist, wird erfindungsgemäß so verfahren, daß die zu jedem Zeitpunkt ab Beginn der erfindinngsgemäßen radikalischen wäßrigen Emulsionspolymerisation im Polymerisationsgefäß enthaltene Menge an Dispergiermittel, auf die Summe der dem Polymerisationsgefäß bereits zugeführten Massen an Ausgangspolymerisat I und zu polymerisierenden Monomeren bezogen, 0,5 bis 5 Gew.-% beträgt.If this is the case, the procedure according to the invention is such that the free-radical aqueous emulsion polymerization in the polymerization vessel at any time from the start of the invention contained amount of dispersant, based on the sum of the masses of starting polymer I and monomers to be polymerized, which have already been fed to the polymerization vessel, is 0.5 to 5% by weight.
Selbstverständlich kann sich im Verlauf der erfindungsgemäßen wäßrigen radikalischen Emulsionspolymerisation während des Zulaufverfahrens die Zusammensetzung der zuzuführenden Monomeren ändern. Ferner kann der Zulauf sowohl stufenförmig als auch kontinuierlich oder nach der Gradientenfahrweise erfolgen. Vorzugsweise erfolgt der Monomerenzulauf kontinuierlich.Of course, the composition of the monomers to be fed can change in the course of the aqueous radical emulsion polymerization according to the invention during the feed process. Furthermore, the inflow can take place stepwise or continuously or according to the gradient procedure. The monomer feed is preferably carried out continuously.
Nach Beendigung des eigentlichen erfindinngsgemäßen Polymerisationsverfahrens wird vorzugsweise noch einige Stunden unter Aufrechterhaltung der Polymerisationstemperatur nachgerührt. Daran können sich übliche Maßnahmen zur Restmonomerenentfernung, zur Einstellung eines anderen pH-Wertes oder sonstige Methoden zur Nachstabilisierung, inklusive nachträglicher Zugabe an Dispergiermitteln, anschließen. Selbstverständlich können die verschiedenen möglichen, in der Regel räumlich getrennt erfolgenden, Zuläufe unmittelbar vor Eintritt in das Polymerisationsgefäß miteinander vermischt werden.After the actual polymerization process according to the invention has ended, stirring is preferably continued for a few hours while maintaining the polymerization temperature. This can be followed by customary measures for removing residual monomers, adjusting a different pH or other methods for post-stabilization, including the subsequent addition of dispersants. Of course, the various possible, usually spatially separate, feeds can be mixed with one another immediately before entering the polymerization vessel.
Bevorzugte Klassen von Endpolymerisaten sind solche, die
- zu 70 bis 100 Gew.-% aus Estern der Acryl- und/oder Methacrylsäure mit 1 bis 12 C-Atome aufweisenden Alkanolen und/oder Styrol
- zu 70 bis 100 Gew.-% aus Styrol und/oder Butadien aufgebaut sind, wobei die Klasse der Acrylate besonders bevorzugt ist und vorzugsweise nachfolgende Monomerenzusammensetzung umfaßt:
70 bis 99 Gew.-% wenigstens eines Esters der Acryl- und/oder Methacrylsäure mit 1 bis 8 C-Atome aufweisenden Alkanolen,
1 bis 5 Gew.-% Acrylsäure, Methacrylsäure oder deren Gemisch und
0 bis 25 Gew.-% Vinylacetat, Styrol oder deren Gemisch.
- 70 to 100% by weight of esters of acrylic and / or methacrylic acid with alkanols and / or styrene having 1 to 12 carbon atoms
- 70 to 100% by weight are composed of styrene and / or butadiene, the class of acrylates being particularly preferred and preferably comprising the following monomer composition:
70 to 99% by weight of at least one ester of acrylic and / or methacrylic acid with alkanols having 1 to 8 carbon atoms,
1 to 5 wt .-% acrylic acid, methacrylic acid or a mixture thereof and
0 to 25 wt .-% vinyl acetate, styrene or a mixture thereof.
Bei der erfindungsgemäßen radikalischen wäßrigen Emulsionspolymerisation lassen sich in einfacher Weise wäßrige Polymerisatenddispersionen erhalten, die eine sehr breite Endpolymerisatteilchenverteilung aufweisen, welche in typischer Weise Element der beiden nachfolgenden Teilchenverteilungsraster ist:
- 2 bis 25 Gew.-% des Endpolymerisats ≦ 200 nm
- 10 bis 50 Gew.-% des Endpolymerisats ≦ 300 nm
- 30 bis 75 Gew.-% des Endpolymerisats ≦ 400 nm
- 45 bis 85 Gew.-% des Endpolymerisats ≦ 500 nm
- 100 Gew.-% des Endpolymerisats ≦ 700 nm
- 2 bis 5 Gew.-% des Endpolymerisats ≦ 200 nm
- 8 bis 15 Gew.-% des Endpolymerisats ≦ 300 nm
- 18 bis 45 Gew.-% des Endpolymerisats ≦ 400 nm
- 20 bis 50 Gew.-% des Endpolymerisats ≦ 500 nm
- 22 bis 65 Gew.-% des Endpolymerisats ≦ 600 nm
- 50 bis 85 Gew.-% des Endpolymerisats ≦ 700 nm
- 55 bis 98 Gew.-% des Endpolymerisats ≦ 800 nm
- 100 Gew.-% des Endpolymerisats ≦ 1200 nm
- 2 to 25% by weight of the final polymer ≦ 200 nm
- 10 to 50 wt .-% of the final polymer ≦ 300 nm
- 30 to 75% by weight of the final polymer ≦ 400 nm
- 45 to 85 wt .-% of the final polymer ≦ 500 nm
- 100% by weight of the final polymer ≦ 700 nm
- 2 to 5% by weight of the final polymer ≦ 200 nm
- 8 to 15% by weight of the final polymer ≦ 300 nm
- 18 to 45 wt .-% of the final polymer ≦ 400 nm
- 20 to 50 wt .-% of the final polymer ≦ 500 nm
- 22 to 65% by weight of the final polymer ≦ 600 nm
- 50 to 85% by weight of the final polymer ≦ 700 nm
- 55 to 98% by weight of the final polymer ≦ 800 nm
- 100% by weight of the final polymer ≦ 1200 nm
Diese speziellen Teilchengrößenverteilungen sind vermutlich für den reduzierten Fließwiderstand der erfindinngsgemäßen wäßrigen Polymerisatenddispersionen verantwortlich, die normalerweise Newton'sscher Fließverhalten aufweisen. Unterhalb einer Feststoffvolumenkonzentration von 50 Vol.-% nimmt der Einfluß der Teilchengrößenverteilung auf den Fließwiderstand zunehmend ab. Die erfindinngsgemäßen wäßrigen Polymerisatenddispersionen werden wie beschrieben in der Regel mit voll befriedigender Reproduzierbarkeit und in Abwesenheit von Ausflockungen mit Feststoffvolumenkonzentrationen von bis zu 75 Vol.-% in großtechnisch einfach realisierbarer Weise erhalten.These special particle size distributions are probably responsible for the reduced flow resistance of the aqueous polymer dispersions according to the invention, which normally have Newtonian flow behavior. Below a solid volume concentration of 50% by volume, the influence of the particle size distribution on the flow resistance decreases increasingly. As described, the aqueous polymer dispersions according to the invention are generally obtained with fully satisfactory reproducibility and in the absence of flocculation with solid volume concentrations of up to 75% by volume in a manner which is simple to implement on an industrial scale.
Besonders ausgeprägt entfalten die erfindinngsgemäßen wäßrigen Polymerisatenddispersionen ihre vorteilhaften Eigenschaften bei Feststoffvolumenkonzentrationen oberhalb von 65 Vol.-%, weshalb solche Polymerisatenddispersionen bevorzugt sind. Sie eignen sich generell als Bindemittel sowie als Massen zur Herstellung von Beschichtungen und Verklebungen, wobei diesbezüglich in an sich bekannter Weise zusätzliche Hilfsstoffe wie Filmbildehilfsmittel, Füllstoffe oder Weichmacher zugesetzt werden können.The aqueous polymer final dispersions according to the invention display their advantageous properties at solids volume concentrations above 65% by volume, which is why such polymer final dispersions are preferred are. They are generally suitable as binders and as compositions for the production of coatings and bonds, in this regard additional auxiliaries such as film-forming aids, fillers or plasticizers can be added in a manner known per se.
-
ADII(1): Ein Geisch aus
- 1,44 kg
- n-Butylacrylat
- 16,28 kg
- Wasser
- 1,27 kg
- einer 45 gew.-%igen Dowfax 2A1 entsprechenden grenzflächenaktiven Substanz
- 0,52 kg
- einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung
- Zulauf I:
- 47,0 kg
- Wasser
- 14,7 kg
- n-Butylacrylat
- 14,7 kg
- Methylmethacrylat
- 0,60 kg
- Methacrylsäure
- 0,664 kg
- einer 45 gew.-%igen wäßrigen Lösung der Dowfax 2A1 entsprechenden grenzflächenaktiven Substanz
- Zulauf II:
- 10 kg
- Wasser
- 0,156 kg
- Ascorbinsäure
- 0,004 kg
- Eisen(II)-sulfat.
Es wurde eine wäßrige Dispersion ADII(1) erhalten, die wie folgt charakterisiert ist:
Feststoffgehalt: 30 Gew.-%
- 1.44 kg
- n-butyl acrylate
- 16.28 kg
- water
- 1.27 kg
- a 45 wt% Dowfax 2A1 equivalent surfactant
- 0.52 kg
- a 30 wt .-% aqueous hydrogen peroxide solution
- Inlet I:
- 47.0 kg
- water
- 14.7 kg
- n-butyl acrylate
- 14.7 kg
- Methyl methacrylate
- 0.60 kg
- Methacrylic acid
- 0.664 kg
- a 45% by weight aqueous solution of the surfactant corresponding to Dowfax 2A1
- Inlet II:
- 10 kg
- water
- 0.156 kg
- Ascorbic acid
- 0.004 kg
- Iron (II) sulfate.
An aqueous dispersion ADII (1) was obtained, which is characterized as follows:
Solids content: 30% by weight
-
ADII(2): Ein Gemisch aus
- 521 g
- Wasser
- 12 g
- einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung
- 600 g
- wäßrige Dispersion ADII(1)
- Zulauf I:
- 1176 g
- n-Butylacrylat
- 24 g
- Methacrylsäure
- 30 g
- einer 20 gew.-%igen wäßrigen Lösung eines ethoxylierten Fettalkohols (C18, EO-Grad:18) und
- 60 g
- einer 45 gew.-%igen wäßrigen Lösung der Dowfax 2A1 entsprechenden grenzflächenaktiven Substanz
- Zulauf II:
- 3,6 g
- Ascorbinsäure
- 0,12 g
- Eisen(II)-sulfat
- 400 g
- Wasser.
Es wurde eine wäßrige Dispersion ADII(2) erhalten, die wie folgt charakterisiert ist:
Feststoffgehalt: 40,8 Gew.-%
- 521 g
- water
- 12 g
- a 30 wt .-% aqueous hydrogen peroxide solution
- 600 g
- aqueous dispersion ADII (1)
- Inlet I:
- 1176 g
- n-butyl acrylate
- 24 g
- Methacrylic acid
- 30 g
- a 20% by weight aqueous solution of an ethoxylated fatty alcohol (C 18 , EO grade: 18) and
- 60 g
- a 45% by weight aqueous solution of the surfactant corresponding to Dowfax 2A1
- Inlet II:
- 3.6 g
- Ascorbic acid
- 0.12 g
- Iron (II) sulfate
- 400 g
- Water.
An aqueous dispersion ADII (2) was obtained, which is characterized as follows:
Solids content: 40.8% by weight
-
ADII(3): Wie ADII(2), das vorgelegte Gemisch bestand jedoch aus
- 602 g
- Wasser
- 12 g
- einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung
- 300 g
- wäßrige Dispersion ADII(1).
Die erhaltene wäßrige Dispersion ADII(3) war wie folgt charakterisiert:
Feststoffgehalt: 40,8 Gew.-%
- 602 g
- water
- 12 g
- a 30 wt .-% aqueous hydrogen peroxide solution
- 300 g
- aqueous dispersion ADII (1).
The aqueous dispersion ADII (3) obtained was characterized as follows:
Solids content: 40.8% by weight
-
ADII(4): Wie ADII(2), das vorgelegte Gemisch bestand jedoch aus
- 639 g
- Wasser
- 12 g
- einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung
- 160 g
- wäßrige Dispersion ADII(1).
ADII(4) war wie folgt charakterisiert:
Feststoffgehalt: 40,3 Gew.-%
- 639 g
- water
- 12 g
- a 30 wt .-% aqueous hydrogen peroxide solution
- 160 g
- aqueous dispersion ADII (1).
ADII (4) was characterized as follows:
Solids content: 40.3% by weight
-
ADII(5): Wie ADII(2), das vorgelegte Gemisch bestand jedoch aus
- 661 g
- Wasser
- 12 g
- einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung
- 80 g
- wäßrige Dispersion ADII(1).
ADII(5) war wie folgt charakterisiert:
Feststoffgehalt: 40,7 Gew.-%
- 661 g
- water
- 12 g
- a 30 wt .-% aqueous hydrogen peroxide solution
- 80 g
- aqueous dispersion ADII (1).
ADII (5) was characterized as follows:
Solids content: 40.7% by weight
-
ADII(6): Wie ADII(2), das vorgelegte Gemisch bestand jedoch aus
- 672 g
- Wasser
- 12 g
- einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung
- 40 g
- wäßrige Dispersion ADII(1).
ADII(6) war wie folgt charakterisiert:
Feststoffgehalt: 40,8 Gew.-%
- 672 g
- water
- 12 g
- a 30 wt .-% aqueous hydrogen peroxide solution
- 40 g
- aqueous dispersion ADII (1).
ADII (6) was characterized as follows:
Solids content: 40.8% by weight
-
ADII(7): Wie ADII(2), das vorgelegte Gemisch bestand jedoch aus
- 677 g
- Wasser
- 12 g
- einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung
- 20 g
- wäßrige Dispersion ADII(1).
ADII(7) war wie folgt charakterisiert:
Feststoffgehalt: 41,0 Gew.-%
- 677 g
- water
- 12 g
- a 30 wt .-% aqueous hydrogen peroxide solution
- 20 g
- aqueous dispersion ADII (1).
ADII (7) was characterized as follows:
Solids content: 41.0% by weight
-
ADII(8): Wie ADII(2), das vorgelegte Gemisch bestand jedoch aus
- 680 g
- Wasser
- 12 g
- einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung
- 10 g
- wäßrige Dispersion ADII(1).
ADII(8) war wie folgt charakterisiert:
Feststoffgehalt: 40,7 Gew.-%
- 680 g
- water
- 12 g
- a 30 wt .-% aqueous hydrogen peroxide solution
- 10 g
- aqueous dispersion ADII (1).
ADII (8) was characterized as follows:
Solids content: 40.7% by weight
Die Herstellung der Dispersionen ADI(1) bis ADI(9) erfolgte in einfacher Weise durch Zusammengeben von verschiedenen in Beispiel 1 erhaltenen Dispersionen ADII, wobei die verwendeten Mengen der eingesetzten Dispersionen ADII aus Beispiel 1 so bemessen wurden, daß in den resultierenden Dispersionen ADI die Ausgangspolymerisate APII mit den in der nachfolgenden Tabelle 1 wiedergegebenen Volumenanteilen (Vol.-%, bezogen auf das Gesamtvolumen aller in der jeweiligen Dispersion ADI enthaltenen Ausgangspolymerisate APII) enthalten waren. Demgemäß betrug der Feststoffgehalt der ADI in allen Fällen ca. 40 Gew.-%.
Ein Gemisch aus Wasser, einer 30 gew.-%igen wäßrigen Wasserstoffperoxidlösung, einer Polymerisatausgangsdispersion I aus Beispiel 2 und einem Teil des Zulaufs I wurde auf 70°C erhitzt, und anschließend zeitgleich beginnend die Restmenge des Zulaufs I (innerhalb von 3 h) und Zulauf II (die ersten 10 Gew.-% in 20 min, die restlichen 90 Gew.-% innerhalb von 220 min), unter Aufrechterhaltung der Polymerisationstemperatur, kontinuierlich zugesetzt. Anschließend wurde noch 1 h bei 70°C nachgerührt.A mixture of water, a 30% strength by weight aqueous hydrogen peroxide solution, a polymer starting dispersion I from Example 2 and part of feed I was heated to 70 ° C., and then simultaneously the remaining amount of feed I (within 3 h) and Feed II (the first 10% by weight in 20 min, the remaining 90% by weight within 220 min) was added continuously while maintaining the polymerization temperature. The mixture was then stirred at 70 ° C for 1 h.
Die Zusammensetzung von Zulauf I lautete für ED(1) bis ED(10) wie folgt:
- 1960 g
- n-Butylacrylat
- 40 g
- Methacrysäure
- 100 g
- einer 20 gew.-%igen wäßrigen Lösung der Dowfax 2A1 entsprechenden grenzflächenaktiven Substanz,
- 50 g
- einer 20 gew.-%igen wäßrigen Lösung eines ethoxylierten Fettalkohols (C18, EO-Grad:18) und
- W g
- Wasser,
- 1960 g
- n-butyl acrylate
- 40 g
- Methacrylic acid
- 100 g
- a 20% by weight aqueous solution of the surfactant corresponding to Dowfax 2A1,
- 50 g
- a 20% by weight aqueous solution of an ethoxylated fatty alcohol (C 18 , EO grade: 18) and
- W g
- Water,
Für ED(11) bis ED(13) waren die Zuläufe I entsprechend zusammengesetzt, die 1960 g n-Butylacrylat wurden jedoch ersetzt durch
- ED(11):
- 1560 g
- n-Butylacrylat
- 400 g
- Methylmethacrylat
- ED(12):
- 1560 g
- n-Butylacrylat
- 400 g
- Methylacrylat
- ED(13):
- 1560 g
- n-Butylacrylat
- 400 g
- Vinylacetat.
- ED (11):
- 1560 g
- n-butyl acrylate
- 400 g
- Methyl methacrylate
- ED (12):
- 1560 g
- n-butyl acrylate
- 400 g
- Methyl acrylate
- ED (13):
- 1560 g
- n-butyl acrylate
- 400 g
- Vinyl acetate.
Die Zusammensetzung von Zulauf II lautete in allen Fällen:
- 300 g
- Wasser
- 6 g
- Ascorbinsäure
- 0,2 g
- Eisen(II)-sulfat.
- 300 g
- water
- 6 g
- Ascorbic acid
- 0.2 g
- Iron (II) sulfate.
Tabelle 2 gibt die jeweilige Zusammensetzung der Vorlage (Mengenangaben in Gramm), den Feststoffgehalt und die Volumenkonzentration der Enddispersion (Gew.-% bzw. Vol.-%) sowie die dynamischen Viskositäten η60 und η60,9 von auf einheitliche 60 Gew.-% beziehungsweise 60,9 Vol.-% verdünnten wäßrigen Polymerisatenddispersionen in mPa·s wieder, wobei die η-Bestimmungen gemäß DIN 53019 bei 23°C und einem Schergefälle von 487 s-1 erfolgten.Table 2 gives the respective composition of the initial charge (quantities in grams), the solids content and the volume concentration of the final dispersion (% by weight and% by volume) as well as the dynamic viscosities η 60 and η 60.9 from to a uniform 60%. % or 60.9% by volume of dilute aqueous polymer dispersions in mPas again, the η determinations according to DIN 53019 being carried out at 23 ° C. and a shear rate of 487 s -1 .
Tabelle 3 gibt zusätzlich die Endpolymerisatteilchengrößenverteilung wieder (Gew.-% der Teilchen des Endpolymerisats, deren Teilchendurchmesser ≦ X nm ist, wobei X ein Element aus der Menge {200, 300, 400, 500, 600, 700, 800, 900, 1000, 1200} ist).
Claims (9)
- A final aqueous polymer dispersion having a solids volume concentration of at least 50 % by volume, obtainable by polymerizing at least one radical polymerizable monomer other than a vinyl or vinylidene halide with the addition of at least one aqueous starting polymer dispersion I in a polymerization vessel by the method of free radical aqueous emulsion polymerization in the presence of dispersants and free radical polymerization initiators with the proviso thatA) the mass of polymer contained in the at least one aqueous starting polymer dispersion I added relative to the total mass comprising the mass of the at least one radical polymerizable monomer and the mass of polymer added in the form of the aqueous starting polymer dispersion I is from 1 to 10 %, preferably from 1 to 5 %,B) the at least one aqueous starting polymer dispersion I added is constituted like an aqueous polymer dispersion obtained by adding together n aqueous starting polymer dispersions II with the proviso thata) n is an integer ≧ 2,b) the weight average particle diameter of the starting polymer particles present in dispersion in the respective aqueous starting polymer dispersions II is for every aqueous starting polymer dispersion II within the range > 0 to 400 nm,c) the weight average particle diameter of the starting polymer particles of at least one aqueous starting polymer dispersion II is within the range > 0 to 100 nm,d) the aqueous starting polymer dispersions II have a monomodal distribution of the diameters of the starting polymer particles they contain such that, if dX defines the diameter below which is the particle diameter of X % by weight of all the starting polymer particles present in the particular aqueous starting dispersion II, the ratio (d90-d10)/d50 is from 0.1 to 0.6,e) the relation between the volume Vi, obtainable by dividing the mass of the i-th starting polymer II present in the i-th aqueous starting polymer dispersion II by the mass density of the i-th starting polymer II, and the similarly determined volume Vj, providing that not only the weight average particle diameter (f) the relation between the weight average particle diameter (Vi is the mass of the starting polymer present in the i-th aqueous starting polymer dispersion II divided by the mass density of the starting polymer,V≦100 is the mass of the starting polymer present in the total amount of all aqueous starting polymer dispersions II that have a weight average particle diameter of the starting polymer particles they contain within the range from > 0 to ≦ 100 nm, divided by the mass density of the starting polymer,g) V≦100 is from 0.3 to 10 % by volume, based on the sum of all Vi, andC) the total amount of the at least one aqueous starting polymer dispersion I to be added is introduced into the polymerization vessel as initial charge prior to the start of the free radical aqueous emulsion polymerization, andD) the free radical aqueous emulsion polymerization of the at least one radical polymerizable monomer is effected by the stream addition method with the proviso that- from the start of the free radical aqueous emulsion polymerization the addition of the at least one radical polymerizable monomer to the polymerization vessel is effected in such a way that at any time of the addition the polymerization conversion of the total monomers already added previously to the polymerization vessel is at least 80 mol %, and- the amount of dispersant present in the polymerization vessel is at any time from the start of the free radical aqueous emulsion polymerization from 0.5 to 5 % by weight, based on the sum of the masses of starting polymer I and the monomers to be polymerized already added to the polymerization vessel.
- A final aqueous polymer dispersion as claimed in claim 1, obtainable when the at least one aqueous starting polymer dispersion I used contains of aqueous starting polymer dispersions II where
- A final aqueous polymer dispersion as claimed in claim 1 or 2, obtainable when the at least one aqueous starting polymer dispersion I used contains only such aqueous starting polymer dispersions II that the difference between
- A final aqueous polymer dispersion as claimed in any of claims 1 to 3, obtainable when the at least one aqueous starting polymer dispersion I used has k values within the range from 0.9 to 1.1 and k' values within the range from 0.75 to 3.
- A final aqueous polymer dispersion as claimed in any of claims 1 to 4, obtainable when the at least one aqueous starting polymer dispersion I used has a V≦100 from 0.5 to 5 % by volume, based on the sum of all the Vi it contains.
- An aqueous polymer dispersion as claimed in any of claims 1 to 5, whose solids volume concentration is ≧ 50 % by volume and which has the following polymer particle size distribution:2 - 25 % by weight of polymer ≦ 200 nm10 - 50 % by weight of polymer ≦ 300 nm30 - 75 % by weight of polymer ≦ 400 nm45 - 85 % by weight of polymer ≦ 500 nm100 % by weight of polymer ≦ 700 nm,the polymer containing no vinyl or vinylidene halide.
- An aqueous polymer dispersion as claimed in any of claims 1 to 5, whose solids volume concentration is ≧ 50 % by volume and which has the following polymer particle size distribution:2 - 5 % by weight of polymer ≦ 200 nm8 - 15 % by weight of polymer ≦ 300 nm15 - 45 % by weight of polymer ≦ 400 nm20 - 50 % by weight of polymer ≦ 500 nm22 - 65 % by weight of polymer ≦ 600 nm50 - 85 % by weight of polymer ≦ 700 nm55 - 98 % by weight of polymer ≦ 800 nm100 % by weight of polymer ≦ 1200 nm,the polymer containing no vinyl or vinylidene halide.
- A process for preparing an aqueous polymer dispersion as claimed in claim 1, which comprises polymerizing at least one radical polymerizable monomer other than a vinyl or vinylidene halide with the addition of at least one aqueous starting polymer dispersion I in a polymerization vessel by the method of free radical aqueous emulsion polymerization in the presence of dispersants and free radical polymerization initiators with the proviso thatA) the mass of polymer contained in the at least one aqueous starting polymer dispersion I added relative to the total mass comprising the mass of the at least one radical polymerizable monomer and the mass of polymer added in the form of the aqueous starting polymer dispersion I is from 1 to 10 %, preferably from 1 to 5 %,B) the at least one aqueous starting polymer dispersion I added is constituted like an aqueous polymer dispersion obtained by adding together n aqueous starting polymer dispersions II with the proviso thata) n is an integer ≧ 2,b) the weight average particle diameter of the starting polymer particles present in dispersion in the respective aqueous starting polymer dispersions II is for every aqueous starting polymer dispersion II within the range > 0 to 400 nm,c) the weight average particle diameter of the starting polymer particles of at least one aqueous starting polymer dispersion II is within the range > 0 to 100 nm,d) the aqueous starting polymer dispersions II have a monomodal distribution of the diameters of the starting polymer particles they contain such that, if dX defines the diameter below which is the particle diameter of X % by weight of all the starting polymer particles present in the particular aqueous starting dispersion II, the ratio (d90-d10)/d50 is from 0.1 to 0.6,e) the relation between the volume Vi, obtainable by dividing the mass of the i-th starting polymer II present in the i-th aqueous starting polymer dispersion II by the mass density of the i-th starting polymer II, and the similarly determined volume Vj, providing that not only the weight average particle diameter (f) the relation between the weight average particle diameter (Vi is the mass of the starting polymer present in the i-th aqueous starting polymer dispersion II divided by the mass density of the starting polymer,V≦100 is the mass of the starting polymer present in the total amount of all aqueous starting polymer dispersions II that have a weight average particle diameter of the starting polymer particles they contain within the range from > 0 to ≦ 100 nm, divided by the mass density of the starting polymer,g) V≦100 is from 0.3 to 10 % by volume, based on the sum of all Vi, andC) the total amount of the at least one aqueous starting polymer dispersion I to be added is introduced into the polymerization vessel as initial charge prior to the start of the free radical aqueous emulsion polymerization, andD) the free radical aqueous emulsion polymerization of the at least one radical polymerizable monomer is effected by the stream addition method with the proviso that- from the start of the free radical aqueous emulsion polymerization the addition of the at least one radical polymerizable monomer to the polymerization vessel is effected in such a way that at any time of the addition the polymerization conversion of the total monomers already added previously to the polymerization vessel is at least 80 mol %, and- the amount of dispersant present in the polymerization vessel is at any time from the start of the free radical aqueous emulsion polymerization from 0.5 to 5 % by weight, based on the sum of the masses of starting polymer I and the monomers to be polymerized already added to the polymerization vessel.
- The use of aqueous polymer dispersions as claimed in any of claims 1 to 7 as binders and as materials for preparing coatings and adhesive joints.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4213969A DE4213969A1 (en) | 1992-04-29 | 1992-04-29 | AQUEOUS POLYMER DISPERSION |
DE4213969 | 1992-04-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0567819A1 EP0567819A1 (en) | 1993-11-03 |
EP0567819B1 true EP0567819B1 (en) | 1996-09-04 |
Family
ID=6457666
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93105832A Expired - Lifetime EP0567819B1 (en) | 1992-04-29 | 1993-04-08 | Aqueous polymer dispersion |
Country Status (8)
Country | Link |
---|---|
US (2) | US5426146A (en) |
EP (1) | EP0567819B1 (en) |
JP (1) | JPH0616711A (en) |
CN (1) | CN1051771C (en) |
AU (1) | AU662818B2 (en) |
DE (2) | DE4213969A1 (en) |
ES (1) | ES2090755T3 (en) |
FI (1) | FI931930A (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
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DE4307683A1 (en) * | 1993-03-11 | 1994-09-15 | Basf Ag | Process for the preparation of an aqueous polymer dispersion |
US6130288A (en) † | 1994-09-30 | 2000-10-10 | Nippon Zeon Co Ltd | Copolymer latex and process for producing the same |
DE19624280A1 (en) * | 1996-06-18 | 1998-01-02 | Basf Ag | Process for the preparation of low-viscosity, aqueous polymer dispersions with polymer volume concentrations of at least 50% by volume |
DE19749642A1 (en) | 1997-11-10 | 1999-05-12 | Basf Ag | Use of aqueous preparations which contain a copolymer P as film-forming constituent |
DE19810052A1 (en) * | 1998-03-09 | 1999-09-16 | Basf Ag | Process for coating mineral moldings |
DE19912191C2 (en) | 1999-03-18 | 2001-07-26 | Wacker Chemie Gmbh | Process for the preparation of high solids aqueous polymer dispersions |
DE10035589A1 (en) * | 2000-07-21 | 2002-02-07 | Wacker Polymer Systems Gmbh | Process for the production of polymer dispersions with a high solids content |
AU785016B2 (en) * | 2001-06-14 | 2006-08-24 | Rohm And Haas Company | Semi-continuous bimodal emulsion polymerization |
EP1302515B1 (en) | 2001-10-01 | 2008-08-06 | Rohm And Haas Company | Coating composition based on a bimodal emulsion copolymer, methods of blocking stains, improving hiding, improving block resistance and improving shear stability |
US20030162890A1 (en) * | 2002-02-15 | 2003-08-28 | Kalantar Thomas H. | Nanoscale polymerized hydrocarbon particles and methods of making and using such particles |
DE10337183B4 (en) | 2003-08-13 | 2009-08-06 | Celanese Emulsions Gmbh | Process for the preparation of multimodal polymer dispersions by use of polymeric stabilizers and their use |
US7851348B2 (en) * | 2005-06-14 | 2010-12-14 | Abhay Misra | Routingless chip architecture |
CN101605831B (en) * | 2006-12-19 | 2012-12-26 | 陶氏环球技术有限责任公司 | Ultra-high solid content polyurethane dispersion and continuous process for producing ultra-high solid content polyurethane dispersions |
EP2075263A1 (en) * | 2007-12-17 | 2009-07-01 | Lanxess Inc. | Hydrogenation of a diene-based polymer latex |
EP2072535A1 (en) * | 2007-12-17 | 2009-06-24 | Lanxess Inc. | Hydrogenation of diene-based polymer latex |
EP2528959A1 (en) | 2010-01-25 | 2012-12-05 | Basf Se | Method for producing phenolsulfonic acid aldehyde condensation products and the use thereof as desiccants |
TR201001098A2 (en) | 2010-02-12 | 2010-08-23 | Organi̇k Ki̇mya Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ | Methods and compositions for producing highly active water-based polymer dispersions. |
EP2676970B1 (en) | 2012-06-22 | 2015-04-08 | University Of Waterloo | Hydrogenation of diene-based polymers |
EP2676971B1 (en) | 2012-06-22 | 2015-04-08 | University Of Waterloo | Hydrogenation of a diene-based polymer latex |
EP2676969B1 (en) | 2012-06-22 | 2016-06-01 | University Of Waterloo | Tandem metathesis and hydrogenation of diene-based polymers in latex |
WO2014198022A1 (en) | 2013-06-09 | 2014-12-18 | Lanxess Deutschland Gmbh | Ruthenium- or osmium-based complex catalysts |
KR20200090782A (en) | 2017-12-18 | 2020-07-29 | 아란세오 도이치란드 게엠베하 | Hydrogenation of nitrile butadiene rubber latex |
CN114901703B (en) | 2019-12-31 | 2024-04-23 | 巴斯夫欧洲公司 | Aqueous polymer composition, method for the production thereof and use thereof as a removable pressure-sensitive adhesive |
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US4017442A (en) * | 1975-04-21 | 1977-04-12 | The Dow Chemical Company | Structured-particle latexes |
US4123403A (en) * | 1977-06-27 | 1978-10-31 | The Dow Chemical Company | Continuous process for preparing aqueous polymer microsuspensions |
ZA796171B (en) * | 1978-12-07 | 1980-11-26 | Ici Ltd | Manufacture of polymer dispersions and coating compositions derived from them |
DE3319340A1 (en) * | 1983-05-27 | 1984-11-29 | Röhm GmbH, 6100 Darmstadt | METHOD FOR PRODUCING BI- OR POLYMODAL AQUEOUS PLASTIC DISPERSIONS |
CA1331442C (en) * | 1988-09-16 | 1994-08-16 | Albert S. Will | Fabrication of flexible electronic circuitry using a modified latex polymer laminating adhesive composition |
JPH06102688B2 (en) * | 1989-03-15 | 1994-12-14 | 日本合成ゴム株式会社 | Method for producing polymer particles |
DE4213968A1 (en) * | 1992-04-29 | 1993-11-04 | Basf Ag | AQUEOUS POLYMER DISPERSION |
DE4213964A1 (en) * | 1992-04-29 | 1993-11-04 | Basf Ag | AQUEOUS POLYMER DISPERSIONS |
-
1992
- 1992-04-29 DE DE4213969A patent/DE4213969A1/en not_active Withdrawn
-
1993
- 1993-04-08 ES ES93105832T patent/ES2090755T3/en not_active Expired - Lifetime
- 1993-04-08 DE DE59303617T patent/DE59303617D1/en not_active Expired - Fee Related
- 1993-04-08 EP EP93105832A patent/EP0567819B1/en not_active Expired - Lifetime
- 1993-04-28 AU AU38247/93A patent/AU662818B2/en not_active Ceased
- 1993-04-28 JP JP5102502A patent/JPH0616711A/en active Pending
- 1993-04-29 FI FI931930A patent/FI931930A/en unknown
- 1993-04-29 CN CN93106747A patent/CN1051771C/en not_active Expired - Fee Related
- 1993-12-22 US US08/149,796 patent/US5426146A/en not_active Expired - Lifetime
-
1995
- 1995-01-17 US US08/373,070 patent/US5498655A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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CN1051771C (en) | 2000-04-26 |
DE4213969A1 (en) | 1993-11-04 |
CN1079753A (en) | 1993-12-22 |
AU3824793A (en) | 1993-11-04 |
JPH0616711A (en) | 1994-01-25 |
DE59303617D1 (en) | 1996-10-10 |
ES2090755T3 (en) | 1996-10-16 |
FI931930A0 (en) | 1993-04-29 |
US5426146A (en) | 1995-06-20 |
AU662818B2 (en) | 1995-09-14 |
US5498655A (en) | 1996-03-12 |
FI931930A (en) | 1993-10-30 |
EP0567819A1 (en) | 1993-11-03 |
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